CN116510771A - Preparation method of catalyst for preparing dimethyl ether by low-temperature dehydration of high-water-content methanol and application of catalyst in preparation of dimethyl ether - Google Patents

Preparation method of catalyst for preparing dimethyl ether by low-temperature dehydration of high-water-content methanol and application of catalyst in preparation of dimethyl ether Download PDF

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CN116510771A
CN116510771A CN202310467387.0A CN202310467387A CN116510771A CN 116510771 A CN116510771 A CN 116510771A CN 202310467387 A CN202310467387 A CN 202310467387A CN 116510771 A CN116510771 A CN 116510771A
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methanol
dimethyl ether
catalyst
preparing
water content
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蔡清海
吕泽东
于淼
莫天宇
路嫔
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Harbin Normal University
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Harbin Normal University
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    • 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
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • 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
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
    • 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
    • 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
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/40—Special temperature treatment, i.e. other than just for template removal

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A preparation method of a catalyst for preparing dimethyl ether by low-temperature dehydration of methanol with high water content and application of the catalyst in preparing dimethyl ether relate to a method for preparing dimethyl ether. The invention aims to solve the problems that the prior catalyst can convert methanol into dimethyl ether at a higher reaction temperature, the equipment requirement on the reaction is higher, the cost is high, the selectivity on the dimethyl ether is reduced when the acidity is too strong, the service life of the catalyst is shortened, and the strict requirement on the methanol content is met when the dimethyl ether is prepared. The preparation method comprises the following steps: firstly, immersing NaZSM-5 molecular sieve into aqueous solution of metal salt, stirring for reaction, and then carrying out suction filtration, washing, drying and roasting to obtain the catalyst for preparing dimethyl ether by low-temperature dehydration of methanol with high water content. A catalyst for preparing dimethyl ether by low-temperature dehydration of methanol with high water content is used for preparing dimethyl ether. The invention has the advantages of easily obtained raw materials, simple preparation method, environmental protection and high selectivity of dimethyl ether up to 100 percent.

Description

Preparation method of catalyst for preparing dimethyl ether by low-temperature dehydration of high-water-content methanol and application of catalyst in preparation of dimethyl ether
Technical Field
The invention relates to a method for preparing dimethyl ether.
Background
As fossil fuels are increasingly in shortage of energy and environmental pollution, there is an urgent need to find clean fuels that can replace conventional fossil fuels. Dimethyl ether is currently considered one of the most potential new clean feedstocks because it does not produce pollutants (such as sulfur oxides and nitrogen oxides) and is less carbon monoxide and unburned hydrocarbons when burned.
In the industrial production process, the technology for preparing dimethyl ether mainly adopts a methanol gas phase dehydration method, wherein methanol is gasified in a reactor, and the methanol is dehydrated to synthesize the dimethyl ether through a solid acid catalyst, wherein common solid acid catalysts comprise gamma-Al 2 O 3 Or modified gamma-Al 2 O 3 Acidic zeolite, heteropolyacid and complex oxide etc. (chinese patents CN 111925279A, CN 114249637A, CN 102962100B, CN 104588104A, CN1036199 a). Various catalysts have the advantages but the limitations in preparing the dimethyl ether, and the conventional catalysts all need to convert the methanol into the dimethyl ether at a higher reaction temperature (higher than 220 ℃), so that the requirements on equipment for the reaction are higher, and the investment and the cost are high. The methanol is converted to dimethyl ether at the acid sites with weak acid strength and medium acid strength, because the acid of the acid sites with strong acid strength can promote the formation of a large amount of byproducts, such as hydrocarbon and even carbon deposition, and the catalyst activity is easily and rapidly reduced, thereby reducing the selectivity of the dimethyl ether and the service life of the catalyst and affecting the preparation of the dimethyl ether. Thus, a low-temperature active is developedIs of great significance to the novel catalyst.
According to industrial methanol national standard GB/T338-2011 published in 12 th and 5 th 2011, industrial methanol is classified into three types, the water content of a superior product is 0.1%, the water content of an first-class product is 0.15%, and the water content of an acceptable product is 0.2%, so that the water content of the methanol used for preparing dimethyl ether in the industrial production is extremely low at present; meanwhile, according to chemical equilibrium, the product water generated in the process of preparing dimethyl ether by dehydrating methanol can also inhibit the forward progress of the reaction as a product, and gamma-Al 2 O 3 Hydrophilic, the generated water can be preferentially adsorbed on gamma-Al 2 O 3 The surface can inhibit the adsorption of methanol on the surface of the catalyst, reduce the catalytic activity and influence the service life of the catalyst, and the water content of the methanol is strictly required, so the problem is a problem to be solved in the field.
Disclosure of Invention
The invention aims to solve the problems that the existing catalyst can only convert methanol into dimethyl ether at a higher reaction temperature, the equipment requirement on the reaction is high, the cost is high, the selectivity on dimethyl ether is reduced when the acidity is too strong, the service life of the catalyst is shortened, and the strict requirement on the methanol content is met when the dimethyl ether is prepared, and provides a method for preparing the dimethyl ether by dehydrating the methanol with high water content at a low temperature.
The invention provides a preparation method of a catalyst for preparing dimethyl ether by low-temperature dehydration of high-water-content methanol and application of the catalyst in preparing dimethyl ether. The invention also provides a preparation method of the catalyst, and the surface of the catalyst is modified by utilizing the hydrolysis effect of weak or medium-strength acidic metal salt solution through a simple impregnation method to prepare the composite material with the surface having proper acid and alkali strength.
The preparation method of the catalyst for preparing the dimethyl ether by low-temperature dehydration of the methanol with high water content is completed according to the following steps:
firstly, immersing NaZSM-5 molecular sieve into aqueous solution of metal salt, stirring for reaction, and then carrying out suction filtration, washing, drying and roasting to obtain the catalyst for preparing dimethyl ether by low-temperature dehydration of methanol with high water content.
A catalyst for preparing dimethyl ether by low-temperature dehydration of methanol with high water content is used for preparing dimethyl ether.
The principle of the invention is as follows:
the invention selects NaZSM-5 molecular sieve as a precursor, the molecular sieve NaZSM-5 is immersed in an aqueous solution of a metal salt, and H generated after hydrolysis is generated after the molecular sieve NaZSM-5 is immersed for a certain time + And metal ions are embedded into pore channels and surfaces of the molecular sieve to regulate and modify the acid and the alkali of the surfaces of the molecular sieve catalyst, and then the catalyst is subjected to suction filtration, washing, drying and roasting to obtain the highly dispersed high-water-content methanol dehydration catalyst M/HNaZSM-5 (M is metal) with proper acid and alkali, namely the catalyst for preparing dimethyl ether by low-temperature dehydration of high-water-content methanol.
The invention has the advantages that:
1. in the invention, naZSM-5 molecular sieve is immersed into aqueous solution of metal salt, and part of Na in the molecular sieve NaZSM-5 is immersed into the aqueous solution of metal salt + H produced by hydrolysis of metal ions (Cu, sn, fe, al, cr, co, ni, mn, zn ions) and metal cations in these aqueous metal salts + The surface acidity of the composite material is increased by substitution, so that the prepared catalyst has excellent catalytic performance and anti-carbon deposition performance;
2. the catalyst for preparing the dimethyl ether by the low-temperature dehydration of the high-water-content methanol is suitable for the reaction of preparing the dimethyl ether by the dehydration of the high-water-content methanol, rich acid and alkali active sites are distributed on the surface of the catalyst, the synergism of the surface acid and the alkali ensures that the activity of the dehydration reaction of the high-water-content methanol is still high at a lower temperature, the catalyst can stably run for more than 500 hours, and no carbon deposition is found in the reaction process;
3. the catalyst for preparing the dimethyl ether by low-temperature dehydration of the methanol with high water content has the advantages of easily obtained raw materials, simple preparation method, environmental friendliness, good low-temperature activity in the reaction of preparing the dimethyl ether by the dehydration of the methanol, and high selectivity of the dimethyl ether which can reach 100 percent.
The catalyst for preparing the dimethyl ether by low-temperature dehydration of the methanol with high water content can be obtained.
Drawings
FIG. 1 is a graph showing the conversion rate of dimethyl ether prepared by catalyzing methanol with different water contents by using the catalyst for preparing dimethyl ether by low-temperature dehydration of high-water-content methanol prepared in example 1.
Detailed Description
The first embodiment is as follows: the preparation method of the catalyst for preparing the dimethyl ether by low-temperature dehydration of the methanol with high water content in the embodiment is completed by the following steps:
firstly, immersing NaZSM-5 molecular sieve into aqueous solution of metal salt, stirring for reaction, and then carrying out suction filtration, washing, drying and roasting to obtain the catalyst for preparing dimethyl ether by low-temperature dehydration of methanol with high water content.
The second embodiment is as follows: the present embodiment differs from the specific embodiment in that: the volume ratio of the mass of the metal salt to the water in the aqueous solution of the metal salt is (0.1 g-2 g) 100mL. The other steps are the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from the first or second embodiment in that: the metal salt in the aqueous solution of the metal salt is one or a mixture of a plurality of copper salt, tin salt, ferric salt, aluminum salt, chromium salt, cobalt salt, nickel salt, manganese salt and zinc salt. The other steps are the same as those of the first or second embodiment.
The specific embodiment IV is as follows: one difference between this embodiment and the first to third embodiments is that: the stirring reaction time is 6-24 h, and the stirring reaction speed is 300-1000 r/min. The other steps are the same as those of the first to third embodiments.
Fifth embodiment: one to four differences between the present embodiment and the specific embodiment are: the washing is to use deionized water for 3-5 times. Other steps are the same as those of the first to fourth embodiments.
Specific embodiment six: the present embodiment differs from the first to fifth embodiments in that: the roasting temperature is 200-600 ℃, and the roasting time is 1-5 h. Other steps are the same as those of the first to fifth embodiments.
Seventh embodiment: one difference between the present embodiment and the first to sixth embodiments is that: the roasting temperature is 200-450 ℃. Other steps are the same as those of embodiments one to six.
Eighth embodiment: the embodiment is a catalyst for preparing dimethyl ether by low-temperature dehydration of high-water-content methanol, which is used for preparing dimethyl ether.
Detailed description nine: one of the differences between this embodiment and the first to eighth embodiments is: a catalyst for preparing dimethyl ether by low-temperature dehydration of methanol with high water content is used for preparing dimethyl ether in a high-pressure micro-reaction device, and the specific method is as follows:
a catalyst for preparing dimethyl ether by low-temperature dehydration of methanol with high water content is filled in a fixed bed reactor, and quartz sand with 20-40 meshes is filled at two ends of the catalyst, so that the catalyst is positioned in a reaction constant temperature area; methanol is continuously injected by a microsyringe pump and inert gas N is used 2 As carrier gas, methanol with different water contents is fed into a reactor filled with a catalyst in a gas phase mode for reaction to prepare dimethyl ether, and the reaction product is measured on line by gas chromatography;
the reaction temperature is 155-200 ℃, the reaction pressure is 0.25-1.25 MPa, and the reaction time is 2-24 h; the flow rate of the methanol is 0.01 mL/min-0.05 mL/min. Other steps are the same as those of embodiments one to eight.
The high pressure micro-reverse device (high pressure micro-reverse chromatography system) according to this embodiment is purchased from: beijing Kentun technologies Co.
Detailed description ten: the present embodiment differs from the first to ninth embodiments in that: the reaction temperature is 165-180 ℃; the water content of the methanol is 0.5-50%. The other steps are the same as those of embodiments one to nine.
The following examples are used to verify the benefits of the present invention:
example 1: the preparation method of the catalyst for preparing the dimethyl ether by low-temperature dehydration of the methanol with high water content is completed according to the following steps:
1. adding 1g of copper nitrate into 100mL of distilled water, and stirring at room temperature until the copper nitrate is completely dissolved to obtain an aqueous solution of metal salt;
2. immersing 2g of NaZSM-5 molecular sieve into the aqueous solution of the metal salt, stirring at room temperature for reaction for 15 hours, stopping stirring, performing suction filtration, washing 3 times with distilled water, and then placing the solid substance into an oven and drying at 100 ℃ for 2 hours to obtain a dried precursor; the dried precursor is placed in a muffle furnace and calcined for 3 hours at 300 ℃ to obtain the catalyst (catalyst Cu/NaHZSM-5) for preparing the dimethyl ether by low-temperature dehydration of the methanol with high water content.
Application example 1: tabletting the catalyst for preparing dimethyl ether by low-temperature dehydration of high-water-content methanol prepared in the example 1, grinding and sieving, reserving a 20-40 mesh sample, taking 1g of the catalyst in a fixed bed tubular reactor with an inner diameter of 10mm, and filling quartz sand with equal volume at two ends of the reactor to enable the catalyst to be in a constant temperature zone; n at 180 DEG C 2 Carrying out reaction for 2-20 h in the atmosphere, and measuring the reaction product on line by using gas chromatography; the flow rate of methanol is 0.02mL/min, N 2 The flow rate is 10mL/min, and the reaction pressure is 0.5MPa; in the reaction process, the dehydration reaction process of the methanol is a reaction of generating dimethyl ether by intermolecular dehydration of the methanol, and no byproduct is generated;
the water content of the methanol is 0% (anhydrous methanol), 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 5.0%, 25% or 50%.
The detection method of the reaction product comprises the following steps:
the reaction products were measured by on-line gas chromatography (Shanghai Ling Hua 9890A), FID detector (HP-5 column, 30 m.times.0.32 mm.times.0.25 μm) or gas chromatograph (Agilent 7820), TCD detector (CP-Wax 52CB column, 30 m.times.0.25 mm.times.0.25 μm). The liquid discharged after cooling was subjected to qualitative analysis by gas chromatography-mass spectrometry (Agilent GC7890A-MS 5975C), and the dimethyl ether selectivity and methanol conversion were calculated, and the results are shown in fig. 1. The methyl ether and the methanol respectively show peaks at about 1.928min and 2.949 min. At a lower reaction temperature, in the process of preparing dimethyl ether by dehydrating methanol with high water content, the methanolysis rate is maintained to be above 89% when the water content of the methanol is 5%, the methanolysis rate is maintained to be above 79% when the water content of the methanol is 50%, no byproducts are generated in the reaction process, and the selectivity of the dimethyl ether is 100%.
Example 2: the preparation method of the catalyst for preparing the dimethyl ether by low-temperature dehydration of the methanol with high water content is completed according to the following steps:
1. 1g of SnCl 4 Adding into 100mL distilled water, stirring at room temperature to SnCl 4 Completely dissolving to obtain an aqueous solution of metal salt;
2. immersing 2g of NaZSM-5 molecular sieve into the aqueous solution of the metal salt, stirring at room temperature for reaction for 15 hours, stopping stirring, performing suction filtration, washing 3 times with distilled water, and then placing the solid substance into an oven and drying at 100 ℃ for 2 hours to obtain a dried precursor; the dried precursor is placed in a muffle furnace and calcined at 200 ℃ for 2h, so as to obtain the catalyst (catalyst Sn/NaHZSM-5) for preparing the dimethyl ether by low-temperature dehydration of the methanol with high water content.
Application example 2: tabletting the catalyst for preparing dimethyl ether by low-temperature dehydration of high-water-content methanol prepared in the example 2, grinding and sieving, reserving a 20-40 mesh sample, taking 1g of the catalyst in a fixed bed tubular reactor with an inner diameter of 10mm, and filling quartz sand with equal volume at two ends of the reactor to enable the catalyst to be in a constant temperature zone; n at 170 DEG C 2 Carrying out reaction for 1-22 h in the atmosphere, and measuring the reaction product on line by using gas chromatography; the flow rate of methanol is 0.02mL/min, N 2 The flow rate is 10mL/min, and the reaction pressure is 0.5MPa; in the reaction process, the dehydration reaction process of the methanol is a reaction of generating dimethyl ether by intermolecular dehydration of the methanol, and no byproduct is generated;
the water content of the methanol is 0% (anhydrous methanol), 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 5.0%, 25% or 50%.
The detection method of the reaction product comprises the following steps:
the reaction products were measured by on-line gas chromatography (Shanghai Ling Hua 9890A), FID detector (HP-5 column, 30 m.times.0.32 mm.times.0.25 μm) or gas chromatograph (Agilent 7820), TCD detector (CP-Wax 52CB column, 30 m.times.0.25 mm.times.0.25 μm). The liquid discharged after cooling was subjected to qualitative analysis by gas chromatography-mass spectrometry (Agilent GC7890A-MS 5975C), and the dimethyl ether selectivity and methanol conversion were calculated. The results show that: at a lower reaction temperature, in the process of preparing dimethyl ether by dehydrating methanol with high water content, the conversion rate of the methanol is maintained to be more than 91 percent when the water content of the methanol is 5 percent, the methanolysis rate is maintained to be more than 84 percent when the water content of the methanol is 50 percent, no byproducts are generated in the reaction process, and the selectivity of the dimethyl ether is 100 percent.
Example 3: the preparation method of the catalyst for preparing the dimethyl ether by low-temperature dehydration of the methanol with high water content is completed according to the following steps:
1. adding 1g of ferric nitrate into 100mL of distilled water, and stirring at room temperature until the ferric nitrate is completely dissolved to obtain an aqueous solution of metal salt;
2. immersing 2g of NaZSM-5 molecular sieve into the aqueous solution of the metal salt, stirring at room temperature for reaction for 15 hours, stopping stirring, performing suction filtration, washing 3 times with distilled water, and then placing the solid substance into an oven and drying at 100 ℃ for 2 hours to obtain a dried precursor; the dried precursor is placed in a muffle furnace and calcined for 2h at 450 ℃ to obtain the catalyst (catalyst Fe/NaHZSM-5) for preparing dimethyl ether by low-temperature dehydration of methanol with high water content.
Application example 3: tabletting the catalyst for preparing dimethyl ether by low-temperature dehydration of high-water-content methanol prepared in the embodiment 3, grinding and sieving, reserving a 20-40 mesh sample, taking 1g of the catalyst in a fixed bed tubular reactor with an inner diameter of 10mm, and filling quartz sand with equal volume at two ends of the reactor to enable the catalyst to be in a constant temperature zone; n at 180 DEG C 2 Carrying out reaction for 2-24 h in the atmosphere, and measuring the reaction product on line by using gas chromatography; the flow rate of methanol is 0.02mL/min, N 2 The flow rate is 10mL/min, and the reaction pressure is 0.5MPa; in the reaction process, the dehydration reaction process of the methanol is that the intermolecular dehydration of the methanol generates twoThe reaction of methyl ether does not generate by-products;
the water content of the methanol is 0% (anhydrous methanol), 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 5.0%, 25% or 50%.
The detection method of the reaction product comprises the following steps:
the reaction products were measured by on-line gas chromatography (Shanghai Ling Hua 9890A), FID detector (HP-5 column, 30 m.times.0.32 mm.times.0.25 μm) or gas chromatograph (Agilent 7820), TCD detector (CP-Wax 52CB column, 30 m.times.0.25 mm.times.0.25 μm). The liquid discharged after cooling was subjected to qualitative analysis by gas chromatography-mass spectrometry (Agilent GC7890A-MS 5975C), and the dimethyl ether selectivity and methanol conversion were calculated. The results show that: at a lower reaction temperature, in the process of preparing dimethyl ether by dehydrating methanol with high water content, the conversion rate of the methanol is maintained to be more than 91 percent when the water content of the methanol is 5 percent, the methanolysis rate is maintained to be more than 80 percent when the water content of the methanol is 50 percent, no byproducts are generated in the reaction process, and the selectivity of the dimethyl ether is 100 percent.
Example 4: the preparation method of the catalyst for preparing the dimethyl ether by low-temperature dehydration of the methanol with high water content is completed according to the following steps:
1. adding 1g of aluminum nitrate into 100mL of distilled water, and stirring at room temperature until the aluminum nitrate is completely dissolved to obtain an aqueous solution of metal salt;
2. immersing 2g of NaZSM-5 molecular sieve into the aqueous solution of the metal salt, stirring at room temperature for reaction for 15 hours, stopping stirring, performing suction filtration, washing 3 times with distilled water, and then placing the solid substance into an oven and drying at 100 ℃ for 2 hours to obtain a dried precursor; the dried precursor is placed in a muffle furnace and calcined at 400 ℃ for 3 hours to obtain the catalyst (catalyst Al/NaHZSM-5) for preparing dimethyl ether by low-temperature dehydration of methanol with high water content.
Application example 4: tabletting the catalyst prepared in example 4 and used for preparing dimethyl ether by low-temperature dehydration of methanol with high water content, grinding and sieving, reserving a 20-40 mesh sample, taking 1g of catalyst in a fixed bed tubular reactor with an inner diameter of 10mm, filling quartz sand with equal volume at two ends of the reactor, and keeping the catalyst at constant temperatureA zone; n at 180 DEG C 2 Carrying out reaction for 3-20 h in the atmosphere, and measuring the reaction product on line by using gas chromatography; the flow rate of methanol is 0.02mL/min, N 2 The flow rate is 10mL/min, and the reaction pressure is 0.5MPa; in the reaction process, the dehydration reaction process of the methanol is a reaction of generating dimethyl ether by intermolecular dehydration of the methanol, and no byproduct is generated;
the water content of the methanol is 0% (anhydrous methanol), 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 5.0%, 25% or 50%.
The detection method of the reaction product comprises the following steps:
the reaction products were measured by on-line gas chromatography (Shanghai Ling Hua 9890A), FID detector (HP-5 column, 30 m.times.0.32 mm.times.0.25 μm) or gas chromatograph (Agilent 7820), TCD detector (CP-Wax 52CB column, 30 m.times.0.25 mm.times.0.25 μm). The liquid discharged after cooling was subjected to qualitative analysis by gas chromatography-mass spectrometry (Agilent GC7890A-MS 5975C), and the dimethyl ether selectivity and methanol conversion were calculated. The results show that: at a lower reaction temperature, in the process of preparing dimethyl ether by dehydrating methanol with high water content, the conversion rate of the methanol is maintained above 88% when the water content of the methanol is 5%, the methanolysis rate is maintained above 80% when the water content of the methanol is 50%, no byproducts are generated in the reaction process, and the selectivity of the dimethyl ether is 100%.
Example 5: the preparation method of the catalyst for preparing the dimethyl ether by low-temperature dehydration of the methanol with high water content is completed according to the following steps:
1. adding 1g of chromium nitrate into 100mL of distilled water, and stirring at room temperature until the chromium nitrate is completely dissolved to obtain an aqueous solution of metal salt;
2. immersing 2g of NaZSM-5 molecular sieve into the aqueous solution of the metal salt, stirring at room temperature for reaction for 15 hours, stopping stirring, performing suction filtration, washing 3 times with distilled water, and then placing the solid substance into an oven and drying at 100 ℃ for 2 hours to obtain a dried precursor; the dried precursor is placed in a muffle furnace and calcined for 4 hours at 250 ℃ to obtain the catalyst (catalyst Cr/NaHZSM-5) for preparing dimethyl ether by low-temperature dehydration of methanol with high water content.
Application realityExample 5: tabletting the catalyst for preparing dimethyl ether by low-temperature dehydration of high-water-content methanol prepared in the example 5, grinding and sieving, reserving a 20-40 mesh sample, taking 1g of the catalyst in a fixed bed tubular reactor with an inner diameter of 10mm, and filling quartz sand with equal volume at two ends of the reactor to enable the catalyst to be in a constant temperature zone; n at 175℃ 2 Carrying out reaction for 4-20 h in the atmosphere, and measuring the reaction product on line by using gas chromatography; the flow rate of methanol is 0.02mL/min, N 2 The flow rate is 10mL/min, and the reaction pressure is 0.5MPa; in the reaction process, the dehydration reaction process of the methanol is a reaction of generating dimethyl ether by intermolecular dehydration of the methanol, and no byproduct is generated;
the water content of the methanol is 0% (anhydrous methanol), 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 5.0%, 25% or 50%.
The detection method of the reaction product comprises the following steps:
the reaction products were measured by on-line gas chromatography (Shanghai Ling Hua 9890A), FID detector (HP-5 column, 30 m.times.0.32 mm.times.0.25 μm) or gas chromatograph (Agilent 7820), TCD detector (CP-Wax 52CB column, 30 m.times.0.25 mm.times.0.25 μm). The liquid discharged after cooling was subjected to qualitative analysis by gas chromatography-mass spectrometry (Agilent GC7890A-MS 5975C), and the dimethyl ether selectivity and methanol conversion were calculated. The results show that: at lower reaction temperature, in the process of preparing dimethyl ether by dehydrating methanol with high water content, the conversion rate of the methanol is maintained above 90% when the water content of the methanol is 5%, the methanolysis rate is maintained above 83% when the water content of the methanol is 50%, no byproducts are generated in the reaction process, and the selectivity of the dimethyl ether is 100%.
Example 6: the preparation method of the catalyst for preparing the dimethyl ether by low-temperature dehydration of the methanol with high water content is completed according to the following steps:
1. adding 1g of cobalt nitrate into 100mL of distilled water, and stirring at room temperature until the cobalt nitrate is completely dissolved to obtain an aqueous solution of metal salt;
2. immersing 2g of NaZSM-5 molecular sieve into the aqueous solution of the metal salt, stirring at room temperature for reaction for 15 hours, stopping stirring, performing suction filtration, washing 3 times with distilled water, and then placing the solid substance into an oven and drying at 100 ℃ for 2 hours to obtain a dried precursor; the dried precursor is placed in a muffle furnace and calcined for 2h at 450 ℃ to obtain the catalyst (catalyst Co/NaHZSM-5) for preparing dimethyl ether by low-temperature dehydration of methanol with high water content.
Application example 6: tabletting the catalyst for preparing dimethyl ether by low-temperature dehydration of high-water-content methanol prepared in the example 6, grinding and sieving, reserving a 20-40 mesh sample, taking 1g of the catalyst in a fixed bed tubular reactor with an inner diameter of 10mm, and filling quartz sand with equal volume at two ends of the reactor to enable the catalyst to be in a constant temperature zone; n at 180 DEG C 2 Carrying out reaction for 4-23 h in the atmosphere, and measuring the reaction product on line by using gas chromatography; the flow rate of methanol is 0.02mL/min, N 2 The flow rate is 10mL/min, and the reaction pressure is 0.5MPa; in the reaction process, the dehydration reaction process of the methanol is a reaction of generating dimethyl ether by intermolecular dehydration of the methanol, and no byproduct is generated;
the water content of the methanol is 0% (anhydrous methanol), 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 5.0%, 25% or 50%.
The detection method of the reaction product comprises the following steps:
the reaction products were measured by on-line gas chromatography (Shanghai Ling Hua 9890A), FID detector (HP-5 column, 30 m.times.0.32 mm.times.0.25 μm) or gas chromatograph (Agilent 7820), TCD detector (CP-Wax 52CB column, 30 m.times.0.25 mm.times.0.25 μm). The liquid discharged after cooling was subjected to qualitative analysis by gas chromatography-mass spectrometry (Agilent GC7890A-MS 5975C), and the dimethyl ether selectivity and methanol conversion were calculated. The results show that: at a lower reaction temperature, in the process of preparing dimethyl ether by dehydrating methanol with high water content, the conversion rate of the methanol is maintained to be more than 87.5% when the water content of the methanol is 5%, the methanolysis rate is maintained to be more than 79% when the water content of the methanol is 50%, no byproducts are generated in the reaction process, and the selectivity of the dimethyl ether is 100%.
Example 7: the preparation method of the catalyst for preparing the dimethyl ether by low-temperature dehydration of the methanol with high water content is completed according to the following steps:
1. adding 1g of nickel nitrate into 100mL of distilled water, and stirring at room temperature until the nickel nitrate is completely dissolved to obtain an aqueous solution of metal salt;
2. immersing 2g of NaZSM-5 molecular sieve into the aqueous solution of the metal salt, stirring at room temperature for reaction for 15 hours, stopping stirring, performing suction filtration, washing 3 times with distilled water, and then placing the solid substance into an oven and drying at 100 ℃ for 2 hours to obtain a dried precursor; the dried precursor is placed in a muffle furnace and calcined at 500 ℃ for 2h, so as to obtain the catalyst (catalyst Ni/NaHZSM-5) for preparing the dimethyl ether by low-temperature dehydration of the methanol with high water content.
Application example 7: tabletting the catalyst for preparing dimethyl ether by low-temperature dehydration of high-water-content methanol prepared in the example 7, grinding and sieving, reserving a 20-40 mesh sample, taking 1g of the catalyst in a fixed bed tubular reactor with an inner diameter of 10mm, and filling quartz sand with equal volume at two ends of the reactor to enable the catalyst to be in a constant temperature zone; n at 170 DEG C 2 Carrying out reaction for 2-18 h in the atmosphere, and measuring the reaction product on line by using gas chromatography; the flow rate of methanol is 0.02mL/min, N 2 The flow rate is 10mL/min, and the reaction pressure is 0.5MPa; in the reaction process, the dehydration reaction process of the methanol is a reaction of generating dimethyl ether by intermolecular dehydration of the methanol, and no byproduct is generated;
the water content of the methanol is 0% (anhydrous methanol), 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 5.0%, 25% or 50%.
The detection method of the reaction product comprises the following steps:
the reaction products were measured by on-line gas chromatography (Shanghai Ling Hua 9890A), FID detector (HP-5 column, 30 m.times.0.32 mm.times.0.25 μm) or gas chromatograph (Agilent 7820), TCD detector (CP-Wax 52CB column, 30 m.times.0.25 mm.times.0.25 μm). The liquid discharged after cooling was subjected to qualitative analysis by gas chromatography-mass spectrometry (Agilent GC7890A-MS 5975C), and the dimethyl ether selectivity and methanol conversion were calculated. The results show that: at a lower reaction temperature, in the process of preparing dimethyl ether by dehydrating methanol with high water content, the conversion rate of the methanol is maintained to be more than 87.3 percent when the water content of the methanol is 5 percent, the methanolysis rate is maintained to be more than 79.4 percent when the water content of the methanol is 50 percent, no byproducts are generated in the reaction process, and the selectivity of the dimethyl ether is 100 percent.
Example 8: the preparation method of the catalyst for preparing the dimethyl ether by low-temperature dehydration of the methanol with high water content is completed according to the following steps:
1. adding 1g of zinc nitrate into 100mL of distilled water, and stirring at room temperature until the zinc nitrate is completely dissolved to obtain an aqueous solution of metal salt;
2. immersing 2g of NaZSM-5 molecular sieve into the aqueous solution of the metal salt, stirring at room temperature for reaction for 15 hours, stopping stirring, performing suction filtration, washing 3 times with distilled water, and then placing the solid substance into an oven and drying at 100 ℃ for 2 hours to obtain a dried precursor; the dried precursor is placed in a muffle furnace and calcined for 2h at 450 ℃ to obtain the catalyst (catalyst Zn/NaHZSM-5) for preparing dimethyl ether by low-temperature dehydration of methanol with high water content.
Application example 8: tabletting the catalyst for preparing dimethyl ether by low-temperature dehydration of high-water-content methanol prepared in the example 8, grinding and sieving, reserving a 20-40 mesh sample, taking 1g of the catalyst in a fixed bed tubular reactor with an inner diameter of 10mm, and filling quartz sand with equal volume at two ends of the reactor to enable the catalyst to be in a constant temperature zone; n at 180 DEG C 2 Carrying out reaction for 2-20 h in the atmosphere, and measuring the reaction product on line by using gas chromatography; the flow rate of methanol is 0.02mL/min, N 2 The flow rate is 10mL/min, and the reaction pressure is 0.5MPa; in the reaction process, the dehydration reaction process of the methanol is a reaction of generating dimethyl ether by intermolecular dehydration of the methanol, and no byproduct is generated;
the water content of the methanol is 0% (anhydrous methanol), 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 5.0%, 25% or 50%.
The detection method of the reaction product comprises the following steps:
the reaction products were measured by on-line gas chromatography (Shanghai Ling Hua 9890A), FID detector (HP-5 column, 30 m.times.0.32 mm.times.0.25 μm) or gas chromatograph (Agilent 7820), TCD detector (CP-Wax 52CB column, 30 m.times.0.25 mm.times.0.25 μm). The liquid discharged after cooling was subjected to qualitative analysis by gas chromatography-mass spectrometry (Agilent GC7890A-MS 5975C), and the dimethyl ether selectivity and methanol conversion were calculated. The results show that: at a lower reaction temperature, in the process of preparing dimethyl ether by dehydrating methanol with high water content, the conversion rate of the methanol is maintained to be above 89.2% when the water content of the methanol is 5%, the methanolysis rate is maintained to be above 79.7% when the water content of the methanol is 50%, no byproducts are generated in the reaction process, and the selectivity of the dimethyl ether is 100%.
Example 9: the preparation method of the catalyst for preparing the dimethyl ether by low-temperature dehydration of the methanol with high water content is completed according to the following steps:
1. adding 1g of manganese chloride into 100mL of distilled water, and stirring at room temperature until the manganese chloride is completely dissolved to obtain an aqueous solution of metal salt;
2. immersing 2g of NaZSM-5 molecular sieve into the aqueous solution of the metal salt, stirring at room temperature for reaction for 15 hours, stopping stirring, performing suction filtration, washing 3 times with distilled water, and then placing the solid substance into an oven and drying at 100 ℃ for 2 hours to obtain a dried precursor; the dried precursor is placed in a muffle furnace and calcined at 300 ℃ for 2h, so as to obtain the catalyst (catalyst Mn/NaHZSM-5) for preparing the dimethyl ether by low-temperature dehydration of the methanol with high water content.
Application example 9: tabletting the catalyst for preparing dimethyl ether by low-temperature dehydration of high-water-content methanol prepared in the embodiment 9, grinding and sieving, reserving a 20-40 mesh sample, taking 1g of the catalyst in a fixed bed tubular reactor with an inner diameter of 10mm, and filling quartz sand with equal volume at two ends of the reactor to enable the catalyst to be in a constant temperature zone; n at 175℃ 2 Carrying out reaction for 3-22 h in the atmosphere, and measuring the reaction product on line by using gas chromatography; the flow rate of methanol is 0.02mL/min, N 2 The flow rate is 10mL/min, and the reaction pressure is 0.5MPa; in the reaction process, the dehydration reaction process of the methanol is a reaction of generating dimethyl ether by intermolecular dehydration of the methanol, and no byproduct is generated;
the water content of the methanol is 0% (anhydrous methanol), 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 5.0%, 25% or 50%.
The detection method of the reaction product comprises the following steps:
the reaction products were measured by on-line gas chromatography (Shanghai Ling Hua 9890A), FID detector (HP-5 column, 30 m.times.0.32 mm.times.0.25 μm) or gas chromatograph (Agilent 7820), TCD detector (CP-Wax 52CB column, 30 m.times.0.25 mm.times.0.25 μm). The liquid discharged after cooling was subjected to qualitative analysis by gas chromatography-mass spectrometry (Agilent GC7890A-MS 5975C), and the dimethyl ether selectivity and methanol conversion were calculated. The results show that: at a lower reaction temperature, in the process of preparing dimethyl ether by dehydrating methanol with high water content, the conversion rate of the methanol is maintained above 88.8% when the water content of the methanol is 5%, the methanolysis rate is maintained above 79.6% when the water content of the methanol is 50%, no byproducts are generated in the reaction process, and the selectivity of the dimethyl ether is 100%.

Claims (10)

1. The preparation method of the catalyst for preparing the dimethyl ether by low-temperature dehydration of the methanol with high water content is characterized by comprising the following steps of:
firstly, immersing NaZSM-5 molecular sieve into aqueous solution of metal salt, stirring for reaction, and then carrying out suction filtration, washing, drying and roasting to obtain the catalyst for preparing dimethyl ether by low-temperature dehydration of methanol with high water content.
2. The method for preparing the catalyst for preparing the dimethyl ether by dehydrating the methanol with high water content at low temperature according to claim 1, wherein the volume ratio of the mass of the metal salt to the water in the aqueous solution of the metal salt is (0.1 g-2 g) 100mL.
3. The method for preparing the catalyst for preparing the dimethyl ether by dehydrating the methanol with high water content at low temperature according to claim 1, wherein the metal salt in the aqueous solution of the metal salt is one or a mixture of a plurality of copper salt, tin salt, ferric salt, aluminum salt, chromium salt, cobalt salt, nickel salt, manganese salt and zinc salt.
4. The method for preparing the catalyst for preparing the dimethyl ether by low-temperature dehydration of the methanol with high water content according to claim 1, wherein the stirring reaction time is 6-24 h, and the stirring reaction speed is 300-1000 r/min.
5. The method for preparing the catalyst for preparing the dimethyl ether by low-temperature dehydration of the methanol with high water content according to claim 1, wherein the washing is carried out 3-5 times by using deionized water.
6. The method for preparing the catalyst for preparing the dimethyl ether by low-temperature dehydration of the methanol with high water content according to claim 1, wherein the roasting temperature is 200-600 ℃ and the roasting time is 1-5 h.
7. The method for preparing the catalyst for preparing the dimethyl ether by low-temperature dehydration of the methanol with high water content according to claim 6, wherein the roasting temperature is 200-450 ℃.
8. The use of a catalyst for preparing dimethyl ether by low-temperature dehydration of methanol having a high water content, prepared by the preparation method as claimed in claim 1, characterized in that a catalyst for preparing dimethyl ether by low-temperature dehydration of methanol having a high water content is used for preparing dimethyl ether.
9. The use of a catalyst for the low temperature dehydration of methanol having a high water content for the production of dimethyl ether as claimed in claim 8, wherein the use of a catalyst for the low temperature dehydration of methanol having a high water content for the production of dimethyl ether is carried out in a high pressure micro-reactor, comprising the steps of:
a catalyst for preparing dimethyl ether by low-temperature dehydration of methanol with high water content is filled in a fixed bed reactor, and quartz sand with 20-40 meshes is filled at two ends of the catalyst, so that the catalyst is positioned in a reaction constant temperature area; methanol is continuously injected by a microsyringe pump and inert gas N is used 2 As carrier gas, methanol with different water contents is fed into a reactor filled with a catalyst in a gas phase mode for reaction to prepare dimethyl ether;
the reaction temperature is 155-200 ℃, the reaction pressure is 0.25-1.25 MPa, and the reaction time is 2-24 h; the flow rate of the methanol is 0.01 mL/min-0.05 mL/min.
10. The use of a catalyst for the low temperature dehydration of methanol having a high water content to dimethyl ether as claimed in claim 9, wherein the reaction temperature is 165 ℃ to 180 ℃; the water content of the methanol is 0.5-50%.
CN202310467387.0A 2023-04-26 2023-04-26 Preparation method of catalyst for preparing dimethyl ether by low-temperature dehydration of high-water-content methanol and application of catalyst in preparation of dimethyl ether Pending CN116510771A (en)

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