CN111187239B - Continuous production method of furandicarboxylic acid by taking furan as raw material - Google Patents
Continuous production method of furandicarboxylic acid by taking furan as raw material Download PDFInfo
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- CN111187239B CN111187239B CN202010038860.XA CN202010038860A CN111187239B CN 111187239 B CN111187239 B CN 111187239B CN 202010038860 A CN202010038860 A CN 202010038860A CN 111187239 B CN111187239 B CN 111187239B
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Abstract
The invention discloses a continuous production method of furandicarboxylic acid by taking furan as a raw material, which comprises the following steps: the method comprises the steps that furan serving as a raw material is heated to form gaseous furan, mixed raw material gas formed by mixing the gaseous furan and carbon dioxide enters a fixed bed reactor for reaction, and a transition metal supported catalyst is fixed in the fixed bed reactor; unreacted gaseous furan and carbon dioxide are discharged from an air outlet at the bottom of the fixed bed reactor, and are mixed with mixed raw material gas and then enter the fixed bed reactor from the top end of the fixed bed reactor to react; and discharging furandicarboxylic acid generated by the reaction from a discharge port at the bottom of the reactor. The method for preparing the furandicarboxylic acid has the characteristics of simple process, environment friendliness, high yield and the like.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a continuous production method of furandicarboxylic acid by taking furan as a raw material.
Background
2,5-furandicarboxylic acid (FDCA), also known as anhydromucic acid, is a stable compound that was originally detected in human urine. FDCA has two carboxyl groups in the molecule, can be used as a monomer for polycondensation reaction with glycol or diamine, and can be used for replacing the traditional petroleum-based monomer terephthalic acid to prepare new polymer materials such as polyester, polyamide and the like. The current FDCA material market contains business of hundreds of billions of RMB, including plastics, plasticizers, thermosetting materials, coatings and the like; FDCA is also one of the high value-added bio-based chemicals listed by the U.S. department of energy, and its efficient, green preparation new process research has important economic and social implications.
Currently, there are mainly several routes for the synthesis of FDCA: a 5-Hydroxymethylfurfural (HMF) route, a furoic acid route, a hexenedioic acid cyclization route, a furanacylation route, and the like.
The HMF route is currently widely accepted and almost all commercial studies are underway along this route. However, although the conversion rate of the two steps is very high, the two parts of the catalyst and the reaction conditions are different, and the process problems of difficult separation of the product and the catalyst are added, so that the process integration difficulty is high, and the production efficiency is influenced. Although researchers have developed a one-pot synthesis process from fructose to FDCA, adopts Co-SiO 2 The catalyst (Cooperative effect of cobalt acetylacetonate and silica in the catalytic cyclization and oxidation of fructose to, 5-furandicarboxylic acid.) was not only harsh in reaction conditions (165 ℃,2MPa air), but also the yield of FDCA was lower.
The furoic acid route has few reports at present, furoic acid is prepared by catalytic oxidation of furfural in alkaline solution, whereas the furoic acid to FDCA may undergo disproportionation or carbonylation.
The hexenedioic cyclization route has been reported relatively rarely, and g.bratulescu reports a hexenedioic cyclization reaction catalyzed with benzenesulfonic acid (Cyclization of the D-saccharic acid to2,5-furandicarboxylic acid under the effects of microwaves.) however the yield is only 58%. The raw materials of the route can undergo isomerism and carbonization reactions under acidic conditions, resulting in lower yield.
The furan acylation route is reported to be less. The process of obtaining FDCA by acylation and hydrolysis of furan and oxalyl iodide as raw materials (Preparation method of, 5-furandicarboxylic acid.) has been reported by li et al, but this route has poor atom economy and high raw material cost. J.G.Wang et al report a final FDCA formation process from furan and acetic anhydride by steps such as acetylation and demethylation (From Furan to High Quality Bio-based Poly (ethylene furandicarboxylate)), more steps, poor atom economy and lower yields.
In summary, the reported problems of long reaction route, harsh conditions and the like in a plurality of FDCA production routes relate to route selection and development of a high-efficiency catalytic system for realizing high-efficiency green production of FDCA.
Disclosure of Invention
The invention aims to provide a mild, efficient and clean continuous production method of furan dicarboxylic acid by taking furan as a raw material.
In order to solve the technical problems, the invention provides a continuous production method of furandicarboxylic acid by taking furan as a raw material, which comprises the following steps: the furan as a raw material is heated to form gaseous furan, and the gaseous furan and carbon dioxide are mixed according to the following ratio of 1: 3-5, and the mixed raw material gas enters a fixed bed reactor from the top end of the fixed bed reactor for reaction, wherein a transition metal supported catalyst is fixed in the fixed bed reactor, and the mass ratio of the transition metal supported catalyst to the total amount of furan for reaction is 5-10%; the reaction temperature set in the fixed bed reactor is 100-120 ℃; the reaction pressure is normal pressure; the residence time of the gaseous furan in the fixed bed reactor is 100-150 minutes;
unreacted gaseous furan and carbon dioxide are discharged from a gas outlet at the bottom of the fixed bed reactor, and are mixed with mixed raw material gas (fresh mixed raw material gas) and then enter the fixed bed reactor from the top end of the fixed bed reactor to react (namely, unreacted furan gas and carbon dioxide are subjected to secondary reaction); and discharging furandicarboxylic acid generated by the reaction from a discharge port at the bottom of the reactor.
The improvement of the continuous production method of furan dicarboxylic acid using furan as raw material is as follows: the preparation method of the transition metal supported catalyst comprises the following steps in sequence:
(1) dipping method:
dissolving a soluble salt of a transition metal (as an active center) in water, a transition metal salt solution;
dispersing molecular sieve (as carrier) in water to obtain dispersion;
mixing the transition metal salt solution and the dispersion liquid for 3-6 hours under the stirring condition, and then standing for 1-2 hours;
the weight ratio of the transition metal to the molecular sieve in the soluble salt is 1.0-1.6: 100;
(2) and (3) roasting the precipitate obtained in the step (1) at 400-600 ℃ for 3-5 hours to obtain the transition metal supported catalyst.
Description: the precipitate may be dried conventionally and then calcined.
As a further improvement of the continuous production method of furan dicarboxylic acid using furan as a raw material, the preparation method of the transition metal supported catalyst comprises the following steps:
the transition metal is as follows: nickel (Ni), copper (Cu), rhodium (Rh), palladium (Pd); the soluble salts of the corresponding transition metals are: nickel chloride, copper chloride, rhodium trichloride, and potassium palladium chlorate.
The molecular sieve comprises the following components: 4A type, X type, Y type, ZSM-5 type, al 2 O 3 、SiO 2 、ZrO 2 。Al 2 O 3 、SiO 2 、ZrO 2 Refers to pure Al 2 O 3 Pure SiO 2 Pure ZrO 2 。
In the process of the invention, the inventor comprehensively considers the industrialization difficulty of the reaction process by comparing the reaction characteristics of different routes, and establishes a technical route of continuous production. The invention firstly develops a novel high-efficiency catalyst taking transition metal as an active center, and fixes the transition metal supported catalyst (omega% = 5% -10%) in a fixed bed reactor; placing raw material furan in a furan gas generator, heating to generate furan gas, and introducing the furan gas and carbon dioxide into a fixed bed reactor from the top end of the fixed bed reactor; the catalyst catalyzes 2, 5-dicarbonylation reaction of furan and carbon dioxide to directly generate FDCA, and unreacted furan gas and carbon dioxide are circulated back to the top end of the fixed bed reactor, and enter the reactor together with fresh furan gas and carbon dioxide for secondary reaction until the reaction is complete. The temperature of the fixed bed reactor is between 100 and 120 ℃, and the total yield of the furandicarboxylic acid is more than 95 percent.
The reaction equation of the present invention is as follows:
in the present invention, the weight ratio of transition metal to molecular sieve set according to the present invention, can ensure that all soluble salts of transition metals are adsorbed by the molecular sieve; according to the roasting temperature and time set by the invention, the soluble salts of the transition metals adsorbed on the molecular sieve can be completely converted into the corresponding transition metals.
The production method of furandicarboxylic acid has the following technical advantages:
1. the gas carbon dioxide is used as the raw material, so that the atomic utilization rate is high, no other waste is generated, and the environment-friendly production process is ensured;
2. in the continuous production process, other solvents are not required, so that the production cost can be further reduced;
3. continuous cyclic operation is adopted, the furan reaction is thorough, and the total yield of the product is high; the total yield is more than 95%.
In conclusion, the furandicarboxylic acid prepared by the method has the characteristics of simple process, environmental friendliness, high yield and the like.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a process diagram of a process for the continuous production of furandicarboxylic acid starting from furan according to the invention.
Detailed Description
The invention will be further described with reference to the following specific examples, but the scope of the invention is not limited thereto:
a continuous production device of furan dicarboxylic acid using furan as raw material, as shown in figure 1, comprises a furan gas generator 1 and a fixed bed reactor 2, wherein the outer surface of the fixed bed reactor 2 is provided with a heating sleeve 21, and the heating sleeve 21 is used for controlling the reaction temperature in the fixed bed reactor 2; the side wall of the fixed bed reactor 2 near the bottom is provided with an air outlet 22, and the bottom of the fixed bed reactor 2 is provided with a discharge outlet 23.
Furan as a raw material is placed in a furan gas generator 1 and heated to a gaseous state, mixed raw material gas formed by mixing gaseous furan and carbon dioxide enters a fixed bed reactor 2 from the top end of the fixed bed reactor 2 for reaction, a transition metal supported catalyst is fixed in the fixed bed reactor, the fixed bed reactor 2 is set at a corresponding reaction temperature (100-120 ℃), the reaction pressure is normal pressure, unreacted furan gas and carbon dioxide are discharged from a gas outlet 22 at the bottom of the fixed bed reactor 2, and recycled to the top of the fixed bed reactor 2 and enter the fixed bed reactor 2 together with fresh mixed raw material gas for secondary reaction. The furandicarboxylic acid product is continuously discharged from a discharge port 23 at the bottom of the fixed bed reactor 2.
The following examples all employ the continuous production apparatus.
The furandicarboxylic acid obtained in the following examples had a purity of 99.0% or more.
Example 1, a continuous production method of furandicarboxylic acid, using furan and carbon dioxide as raw materials, sequentially performing the following steps:
1) Preparing Pd/4A type molecular sieve catalyst by an impregnation method: 3.732g of palladium potassium chlorate (containing palladium 1.01 g) is dissolved in 100mL of water, and the solution is fully dispersed; simultaneously, 100g of the 4A type molecular sieve is fully dispersed in 1000mL of water, the two are fully stirred (the rotating speed is about 600 r/min) and mixed for 3h, the mixture is stood for 2h, and the mixture is dried at the temperature of 40 ℃ for 12h in a conventional way and then baked at the temperature of 400 ℃ for 5h, so that about 101g of Pd/4A type molecular sieve catalyst can be obtained.
2) Fixing 100g of the Pd/4A molecular sieve catalyst obtained in the step 1) in a fixed bed reactor 2, adding 1.0kg of furan into a furan gas generator 1, and controlling the gaseous furan and carbon dioxide to be according to 1:3 (as fresh mixed raw material gas) into a fixed bed reactor 2, and the reaction temperature in the fixed bed reactor 2 was set to 100 ℃. Unreacted furan gas and carbon dioxide are discharged from an air outlet 22 at the bottom of the fixed bed reactor 2, circulated to the top of the fixed bed reactor 2 and enter the fixed bed reactor 2 together with fresh mixed raw material gas for secondary reaction. The residence time of the gaseous furan in the fixed bed reactor 2 was 100 minutes; the total yield of furandicarboxylic acid was 2.28kg and was about 98.6%.
Example 2, a continuous production method of furandicarboxylic acid, using furan and carbon dioxide as raw materials, sequentially performing the following steps:
1) Preparation of Ni/Y by impregnation method molecular sieve catalysts: 2.665g of nickel chloride (containing 1.21g of nickel) was dissolved in 100mL of water, and the solution was sufficiently dispersed; simultaneously, fully dispersing 100g of Y-type molecular sieve in 1000mL of water, fully mixing the two for 6h, standing for 1h, drying and roasting at 600 ℃ for 3h to obtain about 101.2g of Ni/Y-type molecular sieve catalyst;
2) Fixing 75g of the Ni/Y type molecular sieve catalyst obtained in the step 1) in a fixed bed reactor 2, adding 1.0kg of furan into a furan gas generator 1, and controlling the gaseous furan and carbon dioxide to be mixed according to the following ratio of 1:5, and then the mixture was fed into a fixed bed reactor 2, wherein the reaction temperature in the fixed bed reactor 2 was set to 120 ℃. Unreacted furan gas and carbon dioxide are discharged from an air outlet 22 at the bottom of the fixed bed reactor 2, circulated to the top of the fixed bed reactor 2 and enter the fixed bed reactor 2 together with fresh mixed raw material gas for secondary reaction. Gaseous furan in fixed bed reactor 2 is 150 minutes; the total yield of furandicarboxylic acid was 2.22kg and was about 95.5%.
Example 3, a continuous production method of furandicarboxylic acid, using furan and carbon dioxide as raw materials, sequentially performing the following steps:
1) Preparing Rh/X type molecular sieve catalyst by an impregnation method: 3.059g of rhodium trichloride (rhodium-containing 1.51 g) was dissolved in 100mL of water, fully dispersing and dissolving; simultaneously, fully dispersing 100g of X-type molecular sieve in 1000mL of water, fully mixing the two, standing for 1.5h, drying and roasting at 500 ℃ for 4.5h to obtain about 101.5g of Rh/X-type molecular sieve catalyst;
2) 50g of Rh/X molecular sieve catalyst obtained in the step 1) is fixed in a fixed bed reactor 2, 1.0kg of furan is added into a furan gas generator 1, and the gaseous furan and carbon dioxide are controlled according to the following formula 1:4 into a fixed bed reactor 2 after being mixed in a molar ratio, and the reaction temperature in the fixed bed reactor 2 is set to be 110 ℃. Unreacted furan gas and carbon dioxide are discharged from an air outlet 22 at the bottom of the fixed bed reactor 2, circulated to the top of the fixed bed reactor 2 and enter the fixed bed reactor 2 together with fresh mixed raw material gas for secondary reaction. The residence time of the gaseous furan in the fixed bed reactor 2 was 120 minutes; the total yield of furandicarboxylic acid was 2.23kg and was about 96.5%.
Example 4, a continuous production method of furandicarboxylic acid, using furan and carbon dioxide as raw materials, sequentially performing the following steps:
1) Pd/Al preparation by impregnation method 2 O 3 Catalyst: 3.732g of palladium potassium chlorate (containing palladium 1.01 g) is dissolved in 100mL of water, and the solution is fully dispersed; at the same time 100g of Al 2 O 3 Dispersing in 1000mL water, mixing the above materials for 4 hr, standing for 2 hr, drying, and calcining at 500deg.C for 4 hr to obtain Pd/Al 2 O 3 About 101.0g of catalyst;
2) Pd/Al obtained in step 1) 2 O 3 100g of catalyst was fixed in a fixed bed reactor 2, 1.0kg of furan was added to a furan gas generator 1, and gaseous furan and carbon dioxide were controlled according to 1:4 into a fixed bed reactor 2 after being mixed in a molar ratio, and the reaction temperature in the fixed bed reactor 2 is set to be 110 ℃. Unreacted furan gas and carbon dioxide are discharged from an air outlet 22 at the bottom of the fixed bed reactor 2, circulated to the top of the fixed bed reactor 2 and enter the fixed bed reactor 2 together with fresh mixed raw material gas for secondary reaction. The residence time of the gaseous furan in the fixed bed reactor 2 was 130 minutes; the total yield of furandicarboxylic acid was 2.26kg and was about 97.7%.
Example 5, a continuous production method of furandicarboxylic acid, using furan and carbon dioxide as raw materials, sequentially performing the following steps:
1) Preparation of Rh/SiO by immersion method 2 Catalyst: 3.059g of rhodium chloride (rhodium-containing 1.51 g) was dissolved in 100mL of water, and the solution was sufficiently dispersed; at the same time 100g of SiO 2 Dispersing in 1000mL water, mixing the above materials for 4 hr, standing for 1.5 hr, drying, and calcining at 400deg.C for 4 hr to obtain Rh/SiO 2 About 101.5g of catalyst;
2) Rh/SiO obtained in step 1) 2 80g of catalyst was fixed in a fixed bed reactor 2, 1.0kg of furan was added to a furan gas generator 1, and gaseous furan and carbon dioxide were controlled according to 1:4 into a fixed bed reactor 2 after being mixed in a molar ratio, and the reaction temperature in the fixed bed reactor 2 is set to be 100 ℃. Unreacted furan gas and carbon dioxide are discharged from an air outlet 22 at the bottom of the fixed bed reactor 2, circulated to the top of the fixed bed reactor 2 and enter the fixed bed reactor 2 together with fresh mixed raw material gas for secondary reaction. The residence time of the gaseous furan in the fixed bed reactor 2 was 140 minutes; 2.20kg of furandicarboxylic acid was obtained in total, the total yield was about 95.1%.
Example 6, a continuous production method of furandicarboxylic acid, using furan and carbon dioxide as raw materials, sequentially performing the following steps:
1) Preparing a Cu/ZSM-5 type molecular sieve catalyst by an impregnation method: 3.125g of copper chloride (containing 1.01g of copper) is dissolved in 100mL of water, and the solution is fully dispersed; simultaneously, fully dispersing 100g of ZSM-5 type molecular sieve in 100mL of water, fully mixing the two materials for 6h, standing for 2h, drying and roasting at 500 ℃ for 5h to obtain about 101.0g of Cu/ZSM-5 type molecular sieve catalyst;
2) Fixing 100g of the Cu/ZSM-5 type molecular sieve obtained in the step 1) in a fixed bed reactor 2, adding 1.0kg of furan into a furan gas generator 1, and controlling the gaseous furan and carbon dioxide to be mixed according to the following ratio of 1:3 into a fixed bed reactor 2 after being mixed in a molar ratio, and the reaction temperature in the fixed bed reactor 2 is set to be 110 ℃. Unreacted furan gas and carbon dioxide are discharged from an air outlet 22 at the bottom of the fixed bed reactor 2, circulated to the top of the fixed bed reactor 2 and enter the fixed bed reactor 2 together with fresh mixed raw material gas for secondary reaction. The residence time of the gaseous furan in the fixed bed reactor 2 was 110 minutes; the total yield of furandicarboxylic acid was 2.23kg and was about 96.6%.
Example 7, a continuous production method of furandicarboxylic acid, using furan and carbon dioxide as raw materials, sequentially performing the following steps:
1) Preparation of Cu/ZrO by impregnation method 2 Catalyst: 3.125g of copper chloride (containing 1.01g of copper) is dissolved in 100mL of water, and the solution is fully dispersed; at the same time, 100g of ZrO 2 Fully dispersing in 100mL of water, fully mixing the two materials for 5h, standing for 2h, drying and roasting at 600 ℃ for 4h to obtain Cu/ZrO 2 About 101.0g of catalyst;
2) Cu/ZrO obtained in step 1) 2 100g of the mixture was fixed in a fixed bed reactor 2, 1.0kg of furan was charged into a furan gas generator 1, and gaseous furan and carbon dioxide were controlled in accordance with 1:5, and then the mixture was fed into a fixed bed reactor 2, wherein the reaction temperature in the fixed bed reactor 2 was set to 120 ℃. Unreacted furan gas and carbon dioxide are discharged from an air outlet 22 at the bottom of the fixed bed reactor 2, circulated to the top of the fixed bed reactor 2 and enter the fixed bed reactor 2 together with fresh mixed raw material gas for secondary reaction. The residence time of the gaseous furan in the fixed bed reactor 2 was 140 minutes; the total yield of furandicarboxylic acid was about 95.4% and 2.20kg was obtained.
Comparative example 1, the reaction temperature in step 2) of example 1 was changed from 100 ℃ to 150 ℃ and the total reaction time was about 15 hours; the remainder was identical to example 1.
The result was that the yield of furandicarboxylic acid was 62.3%.
Comparative example 2, the use of the catalyst in example 1 was omitted, i.e., the fixed bed reactor was not provided with a Pd/4A type molecular sieve catalyst; the remainder was identical to example 1.
The result was that the yield of furandicarboxylic acid was 5.1%.
Comparative example 3,
The catalyst of example 1, step 1) was modified to prepare according to the deposition-precipitation method: 3.732g of palladium potassium chlorate is weighed and dissolved in 100mL of deionized water, and 0.05 mol.L of palladium potassium chlorate is added dropwise under heating and stirring at 60 DEG C -1 Accurately adjusting the pH of the solution using a pH meter=7.5±0.1; then adding 4A type molecular sieve aqueous solution (100 g of 4A type molecular sieve is fully dispersed in 1000mL of water), adjusting the pH value to be 7.5+/-0.1 again, and continuously stirring for 2h; filtering, and filtering cakeWashing with deionized water (3X 50 mL), vacuum drying at 40deg.C for 12h, and roasting in a muffle furnace (400 deg.C and air atmosphere) for 4h to obtain Pd/4A molecular sieve catalyst;
the reaction was carried out with the catalyst obtained according to example 1, step 2).
The result was that the yield of furandicarboxylic acid was 56.6%.
Finally, it should also be noted that the above list is merely a few specific embodiments of the present invention. Obviously, the invention is not limited to the above embodiments, but many variations are possible. All modifications directly derived or suggested to one skilled in the art from the present disclosure should be considered as being within the scope of the present invention.
Claims (1)
1. The continuous production method of 2,5-furandicarboxylic acid using furan as raw material is characterized by comprising the following steps:
the furan as a raw material is heated to form gaseous furan, and the gaseous furan and carbon dioxide are mixed according to the following ratio of 1: 3-5, and the mixed raw material gas enters a fixed bed reactor from the top end of the fixed bed reactor for reaction, wherein a transition metal supported catalyst is fixed in the fixed bed reactor, and the mass ratio of the transition metal supported catalyst to the total amount of furan for reaction is 5-10%; the reaction temperature set in the fixed bed reactor is 100-120 ℃; the reaction pressure is normal pressure; the residence time of the gaseous furan in the fixed bed reactor is 100-150 minutes;
unreacted gaseous furan and carbon dioxide are discharged from an air outlet at the bottom of the fixed bed reactor, and are mixed with mixed raw material gas and then enter the fixed bed reactor from the top end of the fixed bed reactor to react; 2,5-furandicarboxylic acid generated by the reaction is discharged from a discharge port at the bottom of the reactor;
the transition metal supported catalyst is any one of the following: pd/4A type molecular sieve catalyst, ni/Y type molecular sieve catalyst, rh/X type molecular sieve catalyst and Pd/Al 2 O 3 Catalyst, rh/SiO 2 Catalyst, cu/ZSM-5 type molecular sieve catalyst, cu/ZrO 2 A catalyst;
the preparation method of the transition metal supported catalyst comprises the following steps in sequence:
(1) dipping method:
dissolving a soluble salt of a transition metal in water, a transition metal salt solution;
dispersing molecular sieve in water to obtain dispersion;
mixing the transition metal salt solution and the dispersion liquid for 3-6 hours under the stirring condition, and then standing for 1-2 hours;
the weight ratio of the transition metal to the molecular sieve in the soluble salt is 1.0-1.6: 100;
the transition metal is any one of the following: nickel, copper, rhodium, palladium;
the molecular sieve is any one of the following: 4A type, X type, Y type, ZSM-5 type, al 2 O 3 、SiO 2 、ZrO 2，
(2) And (3) roasting the precipitate obtained in the step (1) at 400-600 ℃ for 3-5 hours to obtain the transition metal supported catalyst.
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