CN113731442B - Catalyst for dimethyl maleate hydrogenation reaction and preparation method and application thereof - Google Patents
Catalyst for dimethyl maleate hydrogenation reaction and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of chemical products, and particularly relates to a catalyst for dimethyl maleate hydrogenation reaction, a preparation method and application thereof. The catalyst comprises the following elements in percentage by mole: 30-40% of Cu, 20-30% of Mn, 10-20% of Al, 10-20% of Zn, 0-5% of Ag and 0-5% of Ru. According to the invention, by adding the Al element, the Ag element and the Ru element into the catalyst, the dispersion and modification of active components in the catalyst are realized, the total selectivity of BDO and gamma-butyrolactone can reach 93%, the cost can be effectively reduced, and the catalyst is environment-friendly. The catalyst can be used for preparing 1, 4-butanediol and/or gamma-butyrolactone in a high selectivity way by changing reaction conditions in the process of preparing 1, 4-butanediol by using the catalyst for the hydrogenation reaction of the dimethyl maleate. The preparation method of the catalyst is simple and low in cost, and the prepared catalyst is environment-friendly and has a long service life.
Description
Technical Field
The invention belongs to the technical field of chemical products, and particularly relates to a dimethyl maleate hydrogenation catalyst, a preparation method and application thereof.
Background
1, 4-butanediol is also called BDO, has a plurality of downstream derivatives, is widely used for producing solvents, medicines, cosmetics, plasticizers, curing agents, pesticides and the like, can be used for preparing chemical preparations such as tetrahydrofuran, polybutylene terephthalate, gamma-butyrolactone, N-methylpyrrolidone and the like, and is an important chemical raw material.
At present, the synthesis method of the 1, 4-butanediol mainly comprises the following steps: an alkynal method (Reppe method), a maleic anhydride (maleic anhydride) method, a propylene method, a butadiene method, and the like. Wherein the synthesis route of the maleic anhydride method is to hydrogenate raw material maleic anhydride or dialkyl maleate (such as dimethyl maleate) by a two-step method to prepare the 1, 4-butanediol. The reaction for preparing 1, 4-butanediol by adopting the dialkyl maleate is a gas-phase hydrogenation reaction taking a copper catalyst as a main catalyst. Common copper-based catalysts include chromium-containing catalysts and chromium-free catalysts.
The prior art is not lack of examples of improving the technological conditions of the gas-phase hydrogenation catalytic reaction of the dialkyl maleate and examples of improving the catalyst structure so as to realize high-yield co-production of various products.
For example, patent US5698749 discloses a catalyst with palladium-rhenium supported on a carbon carrier, which can achieve a conversion of dimethyl maleate of 100% under the conditions of 17.3MPa, a temperature of 160 ℃ and a hydrogen carrier gas, but the selectivity to 1, 4-butanediol and tetrahydrofuran is not high, the selectivity to 1, 4-butanediol is only 82.3%, and the selectivity to tetrahydrofuran is only 6.5%.
For another example, patent CN101502803B discloses a catalyst for preparing 1, 4-butanediol by selectively hydrogenating dimethyl maleate, the catalyst uses copper, zinc and aluminum as main elements, manganese, magnesium or chromium is added into the catalyst, the yield of 1, 4-butanediol prepared by hydrogenation can reach 73.6% at the reaction temperature of 180 ℃, the yield of tetrahydrofuran prepared by hydrogenation reaches 96% at the reaction temperature of 220 ℃, and the selectivity of the method to BDO and gamma-butyrolactone is low.
For another example, patent CN1356168A discloses a catalyst for preparing 1, 4-butanediol and co-producing tetrahydrofuran by gas phase hydrogenation of dimethyl maleate, copper, manganese, aluminum and nickel are selected as main elements of the catalyst, and in the reaction of preparing 1, 4-butanediol by catalysis, the selectivity of 1, 4-butanediol is up to 80%, but in the method, the selectivity of 1, 4-butanediol is not high because tetrahydrofuran is co-produced.
In summary, most of the existing gas-phase hydrogenation catalytic processes for dialkyl maleate produce three main products of BDO, gamma-butyrolactone and tetrahydrofuran simultaneously, however, since the economic value of BDO and gamma-butyrolactone is higher and the value of byproduct tetrahydrofuran is not high in the products of the gas-phase hydrogenation catalytic reaction for dialkyl maleate, the gas-phase hydrogenation catalytic process has poor selectivity and can easily produce excessive byproduct tetrahydrofuran, thereby wasting productivity.
Therefore, the reaction for preparing the 1, 4-butanediol by the gas-phase hydrogenation of the dialkyl maleate (such as dimethyl maleate) is improved based on the technical problems in the prior art, and the aim of preparing the catalyst which has high selectivity, high activity, strong adaptability, repeated use and regeneration is fulfilled mainly by adjusting the catalyst structure in the reaction process.
Disclosure of Invention
The invention aims to provide a catalyst for dimethyl maleate hydrogenation reaction, which is characterized in that Al element, ag element and Ru element are added into the catalyst to improve the activity and stability of the catalyst, the total selectivity of BDO and gamma-butyrolactone can reach 93%, the cost can be effectively reduced, and the catalyst is environment-friendly.
The invention also provides application of the catalyst in preparation of 1, 4-butanediol.
Based on the above purpose, the invention adopts the following technical scheme:
the catalyst for the hydrogenation reaction of the dimethyl maleate comprises Cu, mn, al, zn, ag, ru elements, wherein the mole percentages of the elements are as follows: 30-40% of Cu, 20-30% of Mn, 10-20% of Al, 10-20% of Zn, 0-5% of Ag and 0-3% of Ru.
A preparation method of a catalyst for dimethyl maleate hydrogenation reaction comprises the following steps:
(1) Mixing a Cu soluble salt solution, a Zn soluble salt solution and a Mn soluble salt solution to obtain a mixed solution, carrying out parallel flow titration on the mixed solution and a precipitator at the temperature of 70-90 ℃ to carry out coprecipitation reaction, and controlling the total concentration of Cu, mn and Zn metal ions to be 0.7-1.3M; the concentration of the precipitant is 0.8-1.8M, the pH value of a precipitation system is kept at 6.8-7.2, after the dripping is finished, stirring is carried out for 90-120 min at constant temperature, solid-liquid separation is carried out, and then clean water is used for washing, thus obtaining Cu-Mn-Zn-O precipitate;
(2) Adding aluminum hydroxide, silver nitrate, ruthenium chloride and deionized water into the precipitate obtained in the step (1), then heating to the coprecipitation reaction temperature (namely 70-90 ℃) of the mixed solution in the step (1), and stirring and reacting for 55-65 minutes to obtain a solid product;
(3) And (3) drying the solid product obtained in the step (2) at 100-130 ℃, roasting at 350-450 ℃ for 8-12h, tabletting and granulating to obtain the catalyst product.
Specifically, in the step (1), the total concentration of three metal ions Cu, mn and Zn is 0.9-1.1M during the coprecipitation reaction.
Further preferably, in the step (1), hydrogen peroxide is added as a pore-enlarging agent during coprecipitation reaction of the mixed solution and the precipitant solution, and the pore-enlarging agent can change the pores of the catalyst, so that the service life of the catalyst can be prolonged, and the hydrogen peroxide can realize pore-forming in a physical manner between the pores of the catalyst, so that the stability of the catalyst is improved, and meanwhile, the catalyst is more beneficial to energy conservation and environmental protection.
Specifically, the addition amount of the aluminum hydroxide in the step (2) is 10-30% of the total mole number of three metal ions Cu, mn and Zn in the mixed solution; the addition amount of the silver nitrate is 1 to 5 percent of the total mole number of three metal ions of Cu, mn and Zn in the mixed solution; the addition amount of ruthenium chloride is 1-5% of the total mole number of Cu, mn and Zn metal ions in the mixed solution.
Specifically, the added volume of deionized water in the step (2) is 80-120% of the total volume of the mixed solution and the precipitant in the step (1).
Further, the soluble salt solution of Cu, the soluble salt solution of Zn and the soluble salt of Mn may be any one of nitrate, acetate and oxalate, but do not contain Cl and S ions.
Further, the precipitant may be any one of sodium hydroxide, sodium carbonate, ammonia water, oxalic acid.
Further, the catalyst with Cu-Mn-Al-Zn-Ag-Ru-O element prepared by the steps consists of active components of copper, manganese oxide, aluminum oxide, zinc oxide, silver oxide and ruthenium oxide. In the catalyst with Cu-Mn-Al-Zn-Ag-Ru-O element, the metal oxide in the catalyst can disperse and modify the active components. The catalyst is used for the hydrogenation reaction of the dimethyl maleate, and can prepare the 1, 4-butanediol and/or gamma-butyrolactone with high selectivity respectively.
Furthermore, the invention also provides application of the catalyst for the hydrogenation reaction of the dimethyl maleate in preparation of 1, 4-butanediol.
Further preferably, the invention also provides a method for preparing 1, 4-butanediol by using the catalyst for the hydrogenation reaction of the dimethyl maleate, which specifically comprises the following steps:
a. activation of the catalyst: granulating the roasted catalyst powder to 40-60 meshes, and placing the granules in a reaction tube of a fixed bed reactor for reduction and activation treatment;
b. catalytic hydrogenation of dimethyl maleate: and d, placing the dimethyl maleate into a reaction tube in the step a, carrying out catalytic reaction under the conditions of the pressure of 3-5 MPa and the temperature of 170-200 ℃, condensing the reaction product, and collecting the reaction product.
Preferably, the catalytic reaction pressure in step b is 4MPa and the reaction temperature is 180 ℃.
Preferably, the feed rate of dimethyl maleate in step b is from 1 to 2g/h.
Compared with the prior art, the invention has the following advantages:
1. the preparation method of the catalyst is simple and low in cost, and the prepared catalyst is environment-friendly and has a long service life.
2. The invention improves the copper catalyst in the synthesis reaction of 1, 4-butanediol, and realizes the dispersion and modification of active components in the catalyst by adding Al element, ag element and Ru element, thereby improving the activity of the catalyst.
3. The catalyst can be used for preparing 1, 4-butanediol and/or gamma-butyrolactone in a high selectivity way by changing reaction conditions in the process of preparing 1, 4-butanediol by using the catalyst for the hydrogenation reaction of the dimethyl maleate.
The catalyst prepared by the invention not only has higher catalytic activity, but also has good selectivity, the total selectivity of BDO and gamma-butyrolactone can reach 93 percent, the production cost can be effectively reduced, the phenomenon that a plurality of products are produced simultaneously in the gas-phase hydrogenation catalytic reaction of the dialkyl maleate in the prior art, and excessive byproducts are caused is avoided, and the catalyst has good industrial application prospect.
Detailed Description
In order to make the technical objects, technical solutions and advantageous effects of the present invention more apparent, the technical solutions of the present invention will be further described with reference to specific examples, which are intended to illustrate the present invention but are not to be construed as limiting the present invention, and specific techniques or conditions are not specified in the examples, and are performed according to techniques or conditions described in the literature in the art or according to the product specifications.
Example 1
The embodiment prepares a catalyst for the hydrogenation reaction of dimethyl maleate containing Cu, mn, al, zn elements, wherein the mole percentages of the elements are as follows: cu:39.8%, mn:26.86%, zn:16.91%, al:16.43%.
The preparation method of the catalyst for the hydrogenation reaction of the dimethyl maleate comprises the following steps:
(1) 12.0g Cu (NO) 3 ) 2 ·3H 2 O、6g Mn(NO 3 ) 2 And 4g Zn (NO) 3 ) 2 ·6H 2 O is dissolved in 200ml H 2 Preparing a metal ion mixed solution by O; 18g of Na 2 CO 3 Dissolved in 200ml H 2 O is prepared into a precipitator solution;
(2) In a water bath at 80 ℃, the mixed solution of metal ions and the precipitant solution are added in parallel to carry out coprecipitation reaction, the mixture is stirred while being added in a dropwise manner, the pH value of a precipitation system is kept at 6.8, after the dropwise addition is finished, the mixture is stirred at a constant temperature for 90min, and then the mixture is washed by clean water to remove impurity ions, so that a Cu-Mn-Zn-O precipitate is obtained;
(3) 1.6g of Al (OH) was added to the precipitate in step (2) 3 Obtaining a blend, adding 300ml of deionized water into the blend, heating to 80 ℃ and stirring for 60min;
(4) And (3) carrying out suction filtration on the blend in the step (3), carrying out solid-liquid separation, drying the obtained filter cake at 120 ℃ for 12 hours, and then heating to 400 ℃ in a muffle furnace to bake for 10 hours to obtain the catalyst 1 without Ag and Ru.
Example 2
The embodiment prepares a catalyst for the hydrogenation reaction of dimethyl maleate containing Cu, mn, al, zn, ag elements, wherein the mole percentages of the elements are as follows: cu:38.86%, mn:26.23%, zn:16.51%, al:16.04%, ag:2.35%.
The preparation method of the catalyst for the hydrogenation reaction of the dimethyl maleate comprises the following steps:
(1) 12.0g Cu (NO) 3 ) 2 ·3H 2 O、6g Mn(NO 3 ) 2 And 4g Zn (NO) 3 ) 2 ·6H 2 O is dissolved in 200ml H 2 Preparing a metal ion mixed solution by O; 18g of Na 2 CO 3 Dissolved in 200ml H 2 O is prepared into a precipitator solution;
(2) In a water bath at 80 ℃, the mixed solution of metal ions and the precipitant solution are added in parallel to carry out coprecipitation reaction, the mixture is stirred while being added in a dropwise manner, the pH value of a precipitation system is kept at 7, after the dropwise addition is finished, the mixture is stirred at a constant temperature for 100min, and then the mixture is washed by clean water to remove impurity ions, so that a Cu-Mn-Zn-O precipitate is obtained;
(3) 1.6g of Al (OH) was added to the precipitate in step (2) 3 And 0.5g AgNO 3 Obtaining a blend, adding 300ml of deionized water into the blend, heating to 80 ℃ and stirring for 60min;
(4) And (3) carrying out suction filtration on the blend in the step (3), carrying out solid-liquid separation, drying the obtained filter cake at 120 ℃ for 12 hours, and then heating to 400 ℃ in a muffle furnace to bake for 10 hours to obtain the catalyst 2 containing Ag2.35%.
Example 3
The embodiment prepares a catalyst for the hydrogenation reaction of dimethyl maleate containing Cu, mn, al, zn, ru elements, wherein the mole percentages of the elements are as follows: cu:39.17%, mn:26.44%, zn:16.64%, al:16.17%, ru:1.58%.
The preparation method of the catalyst for the hydrogenation reaction of the dimethyl maleate comprises the following steps:
(1) 12.0g Cu (NO) 3 ) 2 ·3H 2 O、6g Mn(NO 3 ) 2 And 4g Zn (NO) 3 ) 2 ·6H 2 O is dissolved in 200ml H 2 Preparing a metal ion mixed solution by O; 18g of Na 2 CO 3 Dissolved in 200ml H 2 O is prepared into a precipitator solution;
(2) In a water bath at 80 ℃, the mixed solution of metal ions and the precipitant solution are added in parallel to carry out coprecipitation reaction, the mixture is stirred while being added in a dropwise manner, the pH value of a precipitation system is kept at 7, after the dropwise addition is finished, the mixture is stirred at a constant temperature for 100min, and then the mixture is washed by clean water to remove impurity ions, so that a Cu-Mn-Zn-O precipitate is obtained;
(3) 1.6g of Al (OH) was added to the precipitate in step (2) 3 And 0.4g RuCl 3 Obtaining a blend, adding 300ml of deionized water into the blend, heating to 80 ℃ and stirring for 60min;
(4) And (3) carrying out suction filtration on the blend in the step (3), carrying out solid-liquid separation, drying the obtained filter cake at 120 ℃ for 12 hours, heating to 400 ℃ in a muffle furnace, and roasting for 10 hours to obtain the catalyst 3 containing Ru1.58%.
Example 4
The embodiment prepares a catalyst for the hydrogenation reaction of dimethyl maleate containing Cu, mn, al, zn, ag, ru elements, wherein the mole percentages of the elements are as follows: cu:38.26%, mn:25.83%, zn:16.26%, al:15.80%, ag:2.31%, ru:1.54%.
The preparation method of the catalyst for the hydrogenation reaction of the dimethyl maleate comprises the following steps:
(1) 12.0g Cu (NO) 3 ) 2 ·3H 2 O、6g Mn(NO 3 ) 2 And 4g Zn (NO) 3 ) 2 ·6H 2 O is dissolved in 200ml H 2 Preparing a metal ion mixed solution by O; 18g of Na 2 CO 3 Dissolved in 200ml H 2 O is prepared into a precipitator solution;
(2) In a water bath at 80 ℃, the mixed solution of metal ions and the precipitant solution are added in parallel to carry out coprecipitation reaction, the mixture is stirred while being added in a dropwise manner, the pH value of a precipitation system is kept at 7.2, after the dropwise addition is finished, the mixture is stirred at a constant temperature for 120min, and then the mixture is washed by clean water to remove impurity ions, so that a Cu-Mn-Zn-O precipitate is obtained;
(3) 1.6g of Al (OH) was added to the precipitate in step (2) 3 、0.5g AgNO 3 、0.4g RuCl 3 Obtaining a blend, adding 300ml of deionized water into the blend, heating to 80 ℃ and stirring for 60min;
(4) And (3) carrying out suction filtration on the blend in the step (3), carrying out solid-liquid separation, drying the obtained filter cake at 120 ℃ for 12 hours, and then heating to 400 ℃ in a muffle furnace to bake for 10 hours to obtain the catalyst 4 containing Ag2.31% and Ru1.54%.
Example 5
The embodiment prepares a catalyst for the hydrogenation reaction of dimethyl maleate containing Cu, mn, al, zn, ag, ru elements, wherein the mole percentages of the elements are as follows: cu:38.26%, mn:25.83%, zn:16.26%, al:15.80%, ag:2.31%, ru:1.54%.
The preparation method of the catalyst for the dimethyl maleate hydrogenation reaction is generally the same as that in the embodiment 4, except that in the step (2), 100g of 28% hydrogen peroxide is added as a pore expanding agent when the mixed solution of metal ions and the solution of precipitant are subjected to co-current flow drop co-precipitation reaction, so that the catalyst 5 is finally obtained.
The pore-expanding agent of hydrogen peroxide used in the embodiment can change the pore space of the catalyst, so that the service life of the catalyst can be prolonged, and the hydrogen peroxide can realize pore-forming in a physical mode between the pore spaces of the catalyst, so that the stability of the catalyst is improved, and meanwhile, the catalyst is more beneficial to energy conservation and environmental protection.
Catalyst Performance test
To verify the activity of the prepared catalyst, the catalyst was used for preparing 1, 4-butanediol by catalytic hydrogenation of dimethyl maleate, and the test procedure was performed using a fixed bed reactor. The specific method comprises the following steps:
a. activating the catalyst: granulating the roasted catalyst powder to 40-60 meshes, loading 10g of catalyst into a reaction tube of a fixed bed reactor, and using N 2 Diluted H 2 The mixed gas (the hydrogen content is 40-60%) is programmed to be heated to 230 ℃ to perform reduction and activation on the catalyst until the hydrogen concentration at the gas inlet and outlet is consistent;
b. catalytic hydrogenation of dimethyl maleate using the activated catalyst: the temperature is increased in the reaction tube under the pressure of 3-5 MPa, preferably 4MPa, the temperature of 170-200 ℃, preferably 180 ℃, the liquid space velocity of 0.2 g/g and the molar ratio of the hydrogen and the ester of 200:1. Then, raw material dimethyl maleate is pumped into a reaction tube through a advection pump, the feeding rate is 2g/h, and the reaction product is collected after condensation and analyzed by gas chromatography.
Table 1 below shows the results of the catalyst prepared in accordance with the present application for the hydrogenation of dimethyl maleate, BDO in Table 1 being 1, 4-butanediol, GBL being gamma-butyrolactone and THF being tetrahydrofuran. The units of the values of the products in Table 1, table 2 and Table 3 are mole percent (mol%) where BDO is 1, 4-butanediol, GBL is gamma-butyrolactone, THF is tetrahydrofuran and DMS is dimethyl succinate.
TABLE 1
The experiment shows that in the catalytic reaction using the catalyst (catalyst 1) containing no Ag and Ru, the reaction is not completely converted, and the BDO+GBL content in the product is low. In the catalytic reaction carried out by using the catalyst (catalyst 2) added with Ag and the catalyst (catalyst 3) added with Ru, the content of BDO+GBL in the product is improved, so that the optimal efficiency of the catalytic reaction can be realized by adding Ag and Ru simultaneously, the catalytic reaction can be nearly completely converted, and the content of BDO+GBL reaches 93.4%.
In the catalytic reaction performed by adding hydrogen peroxide as a pore expanding agent to obtain the catalyst 5, although the content of BDO+GBL in the product is increased compared with that of the catalysts 1-3, the THF content in the product is increased, and the aim of initially reducing the byproduct THF (tetrahydrofuran) cannot be fulfilled. Based on the above data, catalyst 4 is optimally selected, i.e., a catalyst having Cu-Mn-Al-Zn-Ag-Ru-O element.
(II) in order to find the optimal molar content of each element in the catalyst, the invention adjusts the content of Ag and Ru in the catalyst on the basis of the catalyst 4 to obtain the example 6 and the example 7:
example 6
The embodiment prepares a catalyst for the hydrogenation reaction of dimethyl maleate containing Cu, mn, al, zn, ag, ru elements, wherein the mole percentages of the elements are as follows: cu:39.12%, mn:26.41%, zn:16.63%, al:16.16%, ag:0.93%, ru:0.76%.
The preparation method of the catalyst for the hydrogenation reaction of the dimethyl maleate comprises the following steps:
(1) 12g Cu (NO) 3 ) 2 ·3H 2 O、6g Mn(NO 3 ) 2 And 4g Zn (NO) 3 ) 2 ·6H 2 O is dissolved in 200ml H 2 Preparing a metal ion mixed solution by O; 18g of Na 2 CO 3 Dissolved in 200ml H 2 O is prepared into a precipitator solution;
(2) In a water bath at 80 ℃, the mixed solution of metal ions and the precipitant solution are added in parallel to carry out coprecipitation reaction, the mixture is stirred while being added in a dropwise manner, the pH value of a precipitation system is kept at 7.2, after the dropwise addition is finished, the mixture is stirred at a constant temperature for 120min, and then the mixture is washed by clean water to remove impurity ions, so that a Cu-Mn-Zn-O precipitate is obtained;
(3) 1.6g of Al (OH) was added to the precipitate in step (2) 3 、0.2g AgNO 3 、0.2g RuCl 3 Obtaining a blend, adding 300ml of deionized water into the blend, heating to 80 ℃ and stirring for 60min;
(4) And (3) carrying out suction filtration on the blend in the step (3), carrying out solid-liquid separation, drying the obtained filter cake at 120 ℃ for 12 hours, and then heating to 400 ℃ in a muffle furnace to bake for 10 hours to obtain the catalyst 6 containing 2.31% of Ag and 1.54% of Ru.
Example 7
The embodiment prepares a catalyst for the hydrogenation reaction of dimethyl maleate containing Cu, mn, al, zn, ag, ru elements, wherein the mole percentages of the elements are as follows: cu:37.17%, mn:25.09%, zn:15.81%, al:15.35%, ag:4.41%, ru:2.17%.
The preparation method of the catalyst for the hydrogenation reaction of the dimethyl maleate comprises the following steps:
(1) 12.0g Cu (NO) 3 ) 2 ·3H 2 O、6g Mn(NO 3 ) 2 And 4g Zn (NO) 3 ) 2 ·6H 2 O is dissolved in 200ml H 2 Preparing a metal ion mixed solution by O; 18g of Na 2 CO 3 Dissolved in 200ml H 2 O is prepared into a precipitator solution;
(2) In a water bath at 80 ℃, the mixed solution of metal ions and the precipitant solution are added in parallel to carry out coprecipitation reaction, the mixture is stirred while being added in a dropwise manner, the pH value of a precipitation system is kept at 7.2, after the dropwise addition is finished, the mixture is stirred at a constant temperature for 120min, and then the mixture is washed by clean water to remove impurity ions, so that a Cu-Mn-Zn-O precipitate is obtained;
(3) 1.6g of Al (OH) was added to the precipitate in step (2) 3 、1g AgNO 3 、0.6g RuCl 3 Obtaining a blend, adding 300ml of deionized water into the blend, heating to 80 ℃ and stirring for 60min;
(4) And (3) carrying out suction filtration on the blend in the step (3), carrying out solid-liquid separation, drying the obtained filter cake at 120 ℃ for 12 hours, and then heating to 400 ℃ in a muffle furnace to bake for 10 hours to obtain the catalyst 7 containing 2.31% of Ag and 1.54% of Ru.
The method in the test (I) is adopted to catalyze the hydrogenation of the dimethyl maleate to prepare the 1, 4-butanediol, and the catalytic activities of the obtained catalyst 6 and the catalyst 7 are compared with those of the catalyst 4 to obtain the following results shown in the table 2:
TABLE 2
From the data in table 2, it can be seen that the conversion of catalyst 6 (when the Ag and Ru contents are low) was 99%, the conversion was not complete, the THF content of catalyst 7 (when the Ag and Ru contents are high) was high, the bdo+gbl conversion was affected, although the BDO and GBL products obtained in example 7 were less different from those obtained in example 4, and the Ag and Ru contents in the raw materials of catalyst 7 were higher, and catalyst 4 was selected as the most preferable from the viewpoint of cost reduction.
(III) in order to verify the catalytic activity of the catalyst 4 at different temperatures, the invention also adopts a test (I) method to catalyze the hydrogenation of the dimethyl maleate by the catalyst 4 to prepare the 1, 4-butanediol. And the catalyst 4 was evaluated for catalyst activity at different temperatures, and the specific temperatures were 170 ℃, 180 ℃, 190 ℃, 200 ℃ and other reaction conditions were the same as those of the test (one), and the results obtained are shown in the following table 3:
TABLE 3 Table 3
From Table 3, it was found that the amount of THF reaction product was gradually increased with the increase of the reaction temperature, and the reaction temperature was reduced as much as possible in order to minimize the THF yield, but when the temperature was 170 ℃, the conversion of dimethyl maleate was less than 100%, and the conversion was not complete, and the other products were not increased as a whole, so 180℃was selected as the optimum temperature.
Example 8
(IV) to verify the stability of catalyst 4, we have performed a lifetime assessment.
The catalyst evaluation method in test (I) was employed using catalyst 4. Reaction conditions: the pressure is 4MPa, the temperature is 180 ℃, the liquid space velocity is 0.3g/g, and the molar ratio of the hydrogen to the ester is 200:1. The reaction results are: the initial conversion of dimethyl maleate was 100%, BDO selectivity was 89.6%, GBL selectivity was 3.8% and THF selectivity was 3.9%; after 2000 hours of continuous operation, the conversion rate of the dimethyl maleate still can reach 99.5%, the BDO selectivity is 80.6%, the GBL selectivity is 9.8%, and the THF selectivity is 6.4%, and it can be seen that the catalyst activity of the catalyst 4 of the invention is not obviously reduced after long-time operation in the catalytic reaction process, which indicates that the catalyst of the invention has good stability and service life.
Finally, what should be said is: the above embodiments are only for illustrating the technical solution of the present invention, and any equivalent replacement of the present invention and modification or partial replacement without departing from the spirit and scope of the present invention should be covered in the scope of the claims of the present invention.
Claims (10)
1. A catalyst for dimethyl maleate hydrogenation reaction is characterized in that the mole percentage of each element in the catalyst is as follows: 30-40% of Cu, 20-30% of Mn, 10-20% of Al, 10-20% of Zn, 0-5% of Ag and 0-5% of Ru;
the catalyst for the hydrogenation reaction of the dimethyl maleate is prepared by the following steps:
(1) Mixing a Cu soluble salt solution, a Zn soluble salt solution and a Mn soluble salt solution to obtain a mixed solution, performing coprecipitation reaction on the mixed solution and a precipitator at the temperature of 70-90 ℃, and controlling the total concentration of Cu, mn and Zn metal ions to be 0.7-1.3M; the concentration of the precipitant is 0.8-1.8M, the pH value of a precipitation system is kept at 6.8-7.2, after the reaction is finished, stirring is carried out for 90-120 min at constant temperature, and solid-liquid separation is carried out, thus obtaining Cu-Mn-Zn-O precipitate;
(2) Adding aluminum hydroxide, silver nitrate, ruthenium chloride and deionized water into the precipitate obtained in the step (1), heating to 70-90 ℃, and reacting for 55-65min to obtain a solid product;
(3) Drying the solid product obtained in the step (2) at 100-130 ℃, roasting for 8-12 hours at 350-450 ℃, tabletting and granulating to obtain a catalyst product;
in the step (1), the total concentration of three metal ions Cu, mn and Zn is 0.9-1.1M during the coprecipitation reaction;
the addition amount of the aluminum hydroxide in the step (2) is 10-30% of the total mole number of three metal ions of Cu, mn and Zn in the mixed solution; the addition amount of the silver nitrate is 1 to 5 percent of the total mole number of three metal ions of Cu, mn and Zn in the mixed solution; the addition amount of ruthenium chloride is 1-5% of the total mole number of Cu, mn and Zn metal ions in the mixed solution.
2. The method for preparing the catalyst for the hydrogenation reaction of the dimethyl maleate according to claim 1, which is characterized by comprising the following steps:
(1) Mixing a Cu soluble salt solution, a Zn soluble salt solution and a Mn soluble salt solution to obtain a mixed solution, performing coprecipitation reaction on the mixed solution and a precipitator at the temperature of 70-90 ℃, and controlling the total concentration of Cu, mn and Zn metal ions to be 0.7-1.3M; the concentration of the precipitant is 0.8-1.8M, the pH value of a precipitation system is kept at 6.8-7.2, after the reaction is finished, stirring is carried out for 90-120 min at constant temperature, and solid-liquid separation is carried out, thus obtaining Cu-Mn-Zn-O precipitate;
(2) Adding aluminum hydroxide, silver nitrate, ruthenium chloride and deionized water into the precipitate obtained in the step (1), heating to 70-90 ℃, and reacting for 55-65min to obtain a solid product;
(3) And (3) drying the solid product obtained in the step (2) at 100-130 ℃, roasting at 350-450 ℃ for 8-12h, tabletting and granulating to obtain the catalyst product.
3. The preparation method according to claim 2, wherein the total concentration of three metal ions Cu, mn and Zn is 0.9-1.1M in the coprecipitation reaction in the step (1).
4. The method according to claim 2, wherein hydrogen peroxide is added as a pore-enlarging agent in the coprecipitation reaction of the mixed solution and the precipitant solution in the step (1).
5. The preparation method according to claim 2, wherein the addition amount of the aluminum hydroxide in the step (2) is 10-30% of the total mole number of three metal ions of Cu, mn and Zn in the mixed solution; the addition amount of the silver nitrate is 1 to 5 percent of the total mole number of three metal ions of Cu, mn and Zn in the mixed solution; the addition amount of ruthenium chloride is 1-5% of the total mole number of Cu, mn and Zn metal ions in the mixed solution.
6. The preparation method according to claim 2, wherein the added volume of deionized water in the step (2) is 80-120% of the total volume of the mixed solution and the precipitant in the step (1).
7. The production method according to claim 2, wherein the Cu soluble salt solution, zn soluble salt solution, and Mn soluble salt are any one of nitrate, acetate, oxalate; the precipitant is any one of sodium hydroxide, sodium carbonate, ammonia water and oxalic acid.
8. Use of the catalyst for hydrogenation of dimethyl maleate according to claim 1 in the preparation of 1, 4-butanediol.
9. A process for preparing 1, 4-butanediol using the catalyst for the hydrogenation of dimethyl maleate according to claim 1, comprising the steps of:
a. activation of the catalyst: placing a catalyst in a reaction tube for reduction and activation treatment;
b. catalytic hydrogenation of dimethyl maleate: and d, placing the dimethyl maleate into a reaction tube in the step a, carrying out catalytic reaction under the conditions of the pressure of 3-5 MPa and the temperature of 170-200 ℃, condensing the reaction product, and collecting the reaction product.
10. The process of claim 9, wherein the catalytic reaction pressure in step b is 4MPa and the reaction temperature is 180 ℃; the feeding rate of the dimethyl maleate in the step b is 1-2g/h.
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| US8017818B2 (en) * | 2007-03-08 | 2011-09-13 | Virent Energy Systems, Inc. | Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons |
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