CN111659456A - Special catalyst for synthesizing dimethyl carbonate and preparation method thereof - Google Patents

Special catalyst for synthesizing dimethyl carbonate and preparation method thereof Download PDF

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CN111659456A
CN111659456A CN202010529300.4A CN202010529300A CN111659456A CN 111659456 A CN111659456 A CN 111659456A CN 202010529300 A CN202010529300 A CN 202010529300A CN 111659456 A CN111659456 A CN 111659456A
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molecular sieve
catalyst
dimethyl carbonate
synthesizing dimethyl
preparation
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姚元根
郭榕
覃业燕
陈建珊
丁一凡
朱焜
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Fujian Institute of Research on the Structure of Matter of CAS
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/12—Noble metals
    • B01J29/126—Y-type faujasite
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/643—Pore diameter less than 2 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/14—After treatment, characterised by the effect to be obtained to alter the inside of the molecular sieve channels
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions

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Abstract

The invention discloses a special catalyst for synthesizing dimethyl carbonate and a preparation method thereof, wherein the catalyst is represented as PdCu/MxOy-Y, wherein MxOyY represents an oxide modified molecular sieve, an active metal component Pd and an auxiliary agent Cu are loaded on the molecular sieve, the load of Pd is 0.5-1%, and the load of Cu is 1-2%. TheThe preparation of the catalyst is characterized in that the molecular sieve carrier is modified, the molecular sieve is subjected to metal ion exchange, precipitation, roasting and other processes to generate a metal oxide modified molecular sieve surface structure, and the surface acidity of the carrier is reduced compared with that of the traditional Y molecular sieve. The catalyst prepared from the carrier is applied to the process of synthesizing dimethyl carbonate by carbonylation of methyl nitrite, and can effectively inhibit the decomposition of methyl nitrite, thereby improving the selectivity and the space-time yield of the catalyst.

Description

Special catalyst for synthesizing dimethyl carbonate and preparation method thereof
Technical Field
The invention belongs to the technical field of catalysis for synthesizing dimethyl carbonate by carbonylation of methyl nitrite, and particularly relates to a preparation technology of a composite carrier.
Background
Dimethyl Carbonate (DMC) is an important green chemical, and is widely used in the fields of polycarbonate synthesis, electrolyte additives, coatings and the like. At present, dimethyl carbonate is mainly prepared at home and abroad by adopting an ester exchange method, which has the problems of mild reaction conditions and low equipment corrosivity, but has the problems of low conversion rate and high energy consumption. With the continuous development of the market of dimethyl carbonate, the development of a new process route is imperative.
In recent years, the coal chemical industry is continuously developed, coal is used as a raw material, synthesis gas is extracted through conversion, and then different chemicals such as ethanol, ethylene glycol, low-carbon olefin and the like can be produced through a series of reactions. On the basis of the development of the technology for preparing the ethylene glycol from the coal, the technology for preparing the dimethyl carbonate from the coal is carried out. Through the introduction of intermediate methyl nitrite, the carbon monoxide and methyl nitrite can synthesize dimethyl carbonate under the action of a catalyst. In the technology of preparing dimethyl carbonate from coal, the development of a high-efficiency catalyst required for synthesizing dimethyl carbonate is crucial.
Catalysts used in the technology of preparing dimethyl carbonate from coal are mainly divided into two types, one type is a chlorine system catalyst taking activated carbon and lithium aluminum spinel as carriers (U.S. Pat. No. 5,5426209 and U.S. Pat. No. 5,5688984); the other is a chlorine-free system catalyst using Y molecular sieve as carrier (patent CN 1227839A). The catalyst stability is poor due to the problem of chlorine loss of the catalyst containing chlorine system, and the chlorine loss also has certain influence on equipment corrosion. The stability of the catalyst can be improved by a series of chlorine supplementing measures, but the problem of poor stability cannot be thoroughly solved. The chlorine-free system catalyst has excellent stability due to the pore structure characteristics of the molecular sieve, and has the defects of low conversion per pass of carbon monoxide, low selectivity of dimethyl carbonate product and low selectivity, and the problem of low selectivity mainly shows that methyl nitrite is decomposed to generate methanol, Methyl Formate (MF) and Dimethoxymethane (DMM). Aiming at the defects of the catalyst of the chlorine-free system, the design of a novel catalyst is the current research focus.
The McClin subject group at Tianjin university regulates and controls the electron cloud density of the active component Pd by a K additive modification method, and further influences the Activation of Carbon Monoxide (ChemCatchem, Synergy between Palladium and Potasassspeces for Efficient Activation of Carbon Monoxide in the Synthesis of dimethyl Carbonate, 2015, Vol 7, 2460-one 2466). The clever subject group of Fujian substance structure research institute of Chinese academy of sciences prepares the monatomic Pd/NaY catalyst by ion exchange and ammonia evaporation methods, and greatly improves the yield of the chlorine-free system catalyst (ACS catalyst, Synthesis of High-Performance and High-Stability Pd (II)/NaYCatacatalyst for CO Direct Conversion to Dimethyl Carbonate by ratio design, 2019, Vol 9, 3595 3603). In patent 201911100067.1, Yuangen subject group Yao, a institute of Fujian substance Structure, of Chinese academy of sciences, autonomously synthesizes a Y molecular sieve, and modulates a Y molecular sieve skeleton structure by adding components such as titanium, phosphorus and the like, so that the electron cloud density of active components is influenced, the activation of reactant CO is further regulated and controlled, and the catalyst performance is improved. It can be seen that the performance of the chlorine-free system catalyst can be effectively improved by optimally designing the active center, but no clear effective measure exists for the problem of methyl nitrite decomposition at present.
Disclosure of Invention
Aiming at the problem of methyl nitrite decomposition in a chlorine-free system catalyst for synthesizing dimethyl carbonate by using carbon monoxide and methyl nitrite, the invention designs a novel catalyst which can effectively reduce the decomposition of methyl nitrite and improve the selectivity of dimethyl carbonate.
The carbonic acid provided by the inventionThe catalyst special for synthesizing dimethyl ester is PdCu/MxOy-Y, wherein MxOyY represents an oxide modified molecular sieve, an active metal component Pd and an auxiliary agent Cu are loaded on the molecular sieve, the load of Pd is 0.5-1%, and the load of Cu is 1-2%.
The preparation method of the novel carrier provided by the invention comprises the following steps:
A. dissolving soluble metal salt in water to prepare 0.4-1mol/L metal salt solution, adding a commercially available Y-type molecular sieve according to the mass ratio of the metal simple substance to the Y molecular sieve of 0.05-0.2:1, and carrying out ultrasonic treatment for 30-35min to obtain a mixed solution.
The metal salt is one of nitrate, sulfate and chloride of aluminum, titanium, zirconium, lanthanum, cerium and neodymium;
B. slowly dripping alkali solution into the mixed solution under the stirring condition of 30-60 ℃ until metal and alkali completely react to generate precipitate, continuing stirring for 20-30min after the dripping of the alkali solution is finished, performing suction filtration, washing, drying at 100-650 ℃ for 4-8h, and finally roasting at 350-650 ℃ for 4-8h to obtain the oxide modified molecular sieve, which is marked as MxOy-Y。
C. An active metal component Pd and an auxiliary agent Cu are loaded on M by an ion exchange methodxOyLoading the catalyst on Y according to the loading amounts of Pd0.5-1% and Cu 1-2%, and preparing the catalyst expressed as PdCu/MxOy-Y。
The invention disperses exchangeable metal ions by an ultrasonic-assisted ion exchange method, so that the exchangeable metal ions enter a molecular sieve pore passage; the alkali liquor is added to make metal ions form precipitates, and the precipitates can be decomposed by a high-temperature roasting method, so that the Y molecular sieve modified by the metal oxide is formed.
FIGS. 1, 2 and 3 show the comparison of the physicochemical properties of the metal oxide modified Y molecular sieve prepared by the present invention and the unmodified Y molecular sieve.
As can be seen from FIG. 1, in the metal oxide-modified Y molecular sieve, the intensity of the diffraction peak characteristic of the Y molecular sieve is greatly reduced, while the intensity of the diffraction peak characteristic of the corresponding metal oxide is significant, wherein the Nd in example 42O3Easily react with water to generate Nd (OH)3The precipitate is attached to the pore canal of the molecular sieve, so the characteristic peak is attributed to Nd (OH)3. Indicating that the metal oxide was successfully added to the Y molecular sieve structure.
Fig. 2 shows that the pore size of the Y molecular sieve modified by metal oxide is reduced, and the introduction of metal oxide does not significantly increase the mesoporous structure.
From fig. 3, it can be seen that the surface acidity of the Y molecular sieve modified by the metal oxide is significantly changed. The desorption curves of examples 1, 2 and 3 are basically consistent with those of the unmodified Y molecular sieve, but the acid amount is obviously reduced, which shows that the acidity of the surface of the Y molecular sieve can be effectively reduced by proper metal oxide modification. Example 4 has two more desorption peaks at 290 ℃ and 430 ℃, which indicates that the number of strong acid sites in the sample is increased, and this may be related to the generation of Nd (OH) 3.
The catalyst of the invention is mainly used in the process of generating dimethyl carbonate by the reaction of carbon monoxide and methyl nitrite, the table 2 shows the application examination result of the catalyst, and the examination process conditions are as follows: the reaction temperature is 120-140 ℃; the reaction pressure is normal pressure; the space velocity is 2400--1(ii) a The raw material components are respectively CO 10%; CH (CH)3ONO 20-40％；N250-70% by volume. As can be seen from Table 2, the catalyst of the present invention has high selectivity to both carbon monoxide and methyl nitrite, and the space-time yield of dimethyl carbonate reaches about 700 g/(l.h).
The invention has the beneficial effects that: the Y molecular sieve is modified by proper metal oxide, so that the surface structure of the Y molecular sieve is changed, and acid sites on the surface of the molecular sieve can be reduced. The molecular sieve is applied to the process of synthesizing dimethyl carbonate by carbonylation of methyl nitrite, so that the decomposition of the methyl nitrite is effectively inhibited, and the selectivity and the space-time yield of the catalyst are improved.
Drawings
FIG. 1 is an XRD comparison of the sample obtained in step A of examples 1-4 with a commercially available Y molecular sieve, wherein a, b, c, d correspond to the oxide modified Y molecular sieve of step A of examples 1-4, respectively, and e is the commercially available Y molecular sieve.
FIG. 2 is a graph comparing the pore size distribution of the sample obtained in step A of examples 1-4 with that of a commercially available unmodified Y molecular sieve, wherein a, b, c, d correspond to the oxide-modified Y molecular sieve in step A of examples 1-4, respectively, and e is a commercially available Y molecular sieve.
FIG. 3 shows the samples obtained in step A of examples 1-4 and commercial unmodified Y molecular sieve NH3TPD comparison scheme, wherein a, b, c, d correspond to the oxide modified Y molecular sieves of steps A of examples 1-4, respectively, and e is a commercially available Y molecular sieve.
Detailed Description
Example 1
A. Will 8.6gCe (NO3)3·6H2Dissolving O in 50g of water, adding 5g of a commercially available NaY molecular sieve, stirring for 2 hours, dropwise adding 20ml of NaOH solution with the molar concentration of 0.5mol/L at room temperature, continuously stirring for 30 minutes after the alkali solution is dropwise added, performing suction filtration and washing on the mixed solution to obtain a precipitate, drying at 120 ℃ for 4 hours, and roasting at 550 ℃ for 4 hours to obtain an oxide-modified molecular sieve, namely CeO2-Y. The results of the physical property tests are shown in Table 1.
B. Active components Pd and Cu are loaded by an ion exchange method, the loading amounts are Pd 1 percent and Cu 1.5 percent, and the catalyst is prepared and expressed as PdCu/CeO2-Y。
Example 2
A. 3.8g of TiCl4Dissolving in 50g water, adding 5g commercial NaY molecular sieve, stirring for 2h, dripping 10ml NaOH solution with 0.5mol/L molar concentration at room temperature, continuously stirring for 30min after the alkali liquor is dripped, performing suction filtration and washing on the mixed solution to obtain precipitate, drying at 120 ℃ for 4 h, and roasting at 400 ℃ for 4 h to obtain oxide modified molecular sieve TiO2-Y. The results of the physical property tests are shown in Table 1.
B. The active components Pd and Cu are loaded by an ion exchange method, the loading amounts are Pd 1 percent and Cu 1.5 percent, and the catalyst is prepared and is expressed as PdCu/TiO2-Y。
Example 3
A. Mixing 7.5gAl (NO3)2·H2Dissolving O in 50g of water, adding 5g of commercial NaY molecular sieve, and stirring 2Dropping 10ml NaOH solution with the molar concentration of 0.5mol/L at room temperature, continuously stirring for 30min after the alkali liquor is completely dropped, carrying out suction filtration and washing on the mixed solution to obtain a precipitate, drying for 4 hours at 120 ℃, and roasting for 4 hours at 500 ℃ to obtain an oxide modified molecular sieve, Al2O3-Y. The results of the physical property tests are shown in Table 1.
B. The active components Pd and Cu are loaded by an ion exchange method, the loading amounts are Pd 1 percent and Cu 1 percent, and the catalyst is prepared and is expressed as PdCu/Al2O3-Y。
Example 4
A. Will 8.6gNd (NO3)3·6H2Dissolving O in 50g of water, adding 5g of a commercially available NaY molecular sieve, stirring for 2 hours, dropwise adding 20ml of NaOH solution with the molar concentration of 0.5mol/L at room temperature, continuously stirring for 30 minutes after dropwise adding alkali liquor, performing suction filtration and washing on the mixed solution to obtain a precipitate, drying at 120 ℃ for 4 hours, and roasting at 650 ℃ for 4 hours to obtain an oxide modified molecular sieve, Nd2O3-Y. The results of the physical property tests are shown in Table 1.
B. Active components Pd and Cu are loaded by an ion exchange method, the loading amounts are Pd 1 percent and Cu 2 percent, and the catalyst is prepared and is expressed as PdCu/Nd2O3Examples of application of-Y
The results of the physical property tests using a commercial NaY molecular sieve as a comparative sample are shown in table 1. The catalyst was prepared by loading the active components Pd and Cu with the loading amounts of Pd 1% and Cu 1.5%, and expressed as PdCu/Y, and the catalyst PdCu/M prepared in examples 1-4xOyComparative results on-Y are shown in Table 2.
TABLE 1
Sample (I) Ratio of surface product (m)2/g) AveragePore size (nm)
Example 1CeO2-Y 237 0.630
Example 2TiO2-Y 264 0.634
Example 3Al2O3-Y 250 0.630
Example 4Nd2O3-Y 238 0.628
Comparative example Y molecular sieves 453 0.694
Table 1 compares the specific surface area and average pore size of the metal oxide modified Y molecular sieves and unmodified Y molecular sieves. It can be seen that the specific surface area of the Y molecular sieve modified by the metal oxide is reduced, and the average pore diameter is also slightly reduced, which indicates that the metal oxide covers some microporous structures on the surface of the Y molecular sieve. Generally, higher specific surface area means more adsorbable sites, methyl nitrite is excessive in the reaction system, and the methyl nitrite is easily decomposed when adsorbed on the surface of the Y molecular sieve carrier, so that it is advantageous to reduce the specific surface area of the molecular sieve appropriately to improve the selectivity of the catalyst.
The catalysts prepared in examples 1 to 4 and comparative example were subjected to activity evaluation in a continuous flow fixed bed reactor,the tubular reactor had a length of 30cm, an internal diameter of 8mm and a catalyst loading of 5 ml. The reaction uses carbon monoxide and methyl nitrite as raw material gas, nitrogen as diluent gas, and the gas flow rate ratio is N2:CO:CH3ONO (oxide-nitride-oxide) at a ratio of 5-7:1:2-4 and a volume space velocity of 2400--1The reaction temperature is 120-. The composition of the liquid product was analyzed by chromatography and the product comprised dimethyl carbonate (DMC) as the main product, dimethyl oxalate (DMO), Methyl Formate (MF), Dimethoxymethane (DMM) and methanol MeOH as the by-products. From this, the space-time yield STY (g/l.h) of dimethyl carbonate and the selectivity S for carbon monoxide were calculatedCOAnd methyl nitrite selectivity SMNThe calculation method is as follows:
Figure BDA0002534645920000051
Figure BDA0002534645920000052
Figure BDA0002534645920000053
in the formula mDMCIs the number of grams of DMC formed, VcatIs the catalyst loading in liters, t is the reaction time in hours and n is the moles of the corresponding product formed. The results obtained are shown in table 2:
TABLE 2 results of activity calculation of the corresponding catalysts
Figure BDA0002534645920000061
As can be seen from Table 2, the molecular sieve modified by the metal oxide can obviously improve the performance of the catalyst, the conversion rate of carbon monoxide and the selectivity based on methyl nitrite are obviously improved, and the deviation of the selectivity based on carbon monoxide is not large, so that the space-time yield of dimethyl carbonate is also improved.

Claims (2)

1. A preparation method of a special catalyst for synthesizing dimethyl carbonate comprises the following specific preparation steps:
A. dissolving soluble metal salt in water to prepare 0.4-1mol/L metal salt solution, adding a commercially available Y-type molecular sieve according to the mass ratio of the metal simple substance to the Y molecular sieve of 0.05-0.2:1, and carrying out ultrasonic treatment for 30-35min to obtain a mixed solution;
the metal salt is one of nitrate, sulfate and chloride of aluminum, titanium, zirconium, lanthanum, cerium and neodymium;
B. slowly dripping alkali solution into the mixed solution under the stirring condition of 30-60 ℃ until the metal and the alkali completely react to generate precipitate, continuing stirring for 20-30min after the dripping of the alkali solution is finished, performing suction filtration and washing, drying for 4-8h at the temperature of 100-650 ℃, and roasting for 4-8h at the temperature of 350-650 ℃ to obtain the oxide modified molecular sieve, which is marked as MxOy-Y；
C. An active metal component Pd and an auxiliary agent Cu are loaded on M by an ion exchange methodxOyLoading the catalyst on Y according to the loading amounts of Pd0.5-1% and Cu 1-2%, and preparing the catalyst expressed as PdCu/MxOy-Y。
2. The catalyst prepared by the method of claim 1 and used for synthesizing dimethyl carbonate, wherein the catalyst is PdCu/MxOy-Y, wherein MxOyY represents an oxide modified molecular sieve, an active metal component Pd and an auxiliary agent Cu are loaded on the molecular sieve, the load of Pd is 0.5-1%, and the load of Cu is 1-2%.
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