CN107519914A - A kind of molecular sieve catalyst for carbonylation and its preparation method and application - Google Patents
A kind of molecular sieve catalyst for carbonylation and its preparation method and application Download PDFInfo
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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
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/185—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- 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
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- B01J29/24—Iron group metals or copper
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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
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
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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
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
- B01J29/655—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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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
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
- B01J29/66—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing iron group metals, noble metals or copper
- B01J29/68—Iron group metals or copper
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- C—CHEMISTRY; METALLURGY
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide
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Abstract
The present invention relates to a kind of molecular sieve catalyst for carbonylation and its preparation method and application, belong to molecular sieve catalyst technical field.The preparation method of the molecular sieve catalyst for carbonylation of the present invention, comprises the following steps：Hydrogen type molecular sieve is immersed in metal salt solution and carries out ion exchange, is then calcined, then is catalyzed unsaturated hydrocarbons at 400~600 DEG C and carries out carburizing reagent, then pickling is carried out to pre- carbon deposition catalyst using non-oxidizing acid, is produced；The hydrogen type molecular sieve is h-mordenite molecular sieve or the molecular sieves of Hydrogen ZSM 35；A diameter of 0.5~the 0.75nm of molecular dynamics of the unsaturated hydrocarbons.The preparation method of the present invention can eliminate acidic site in large-size duct, while not influence the acidic site in 8 membered ring channels, so as to improve selectivity of the catalyst in preparing methyl acetate by carbonylating dimethyl ether reaction and extend the service life of molecular sieve.
Description
Technical field
The present invention relates to a kind of molecular sieve catalyst for carbonylation and its preparation method and application, belong to molecule
Sieve catalyst technical field.
Background technology
Methyl acetate (methyl acetate) is widely used in the industries such as weaving, spices and medicine, is a kind of important to have
Machine raw material midbody, downstream product mainly have acetic acid, aceticanhydride, methyl acrylate and vinyl acetate, acetamide etc..At home,
The production of methyl acetate is mainly traditional esterifications method.The method exist product separated with catalyst complicated and Noble Metal Rhodium it is expensive with tightly
The problem of lacking, and iodide are serious to equipment corrosion.Solid acid catalysis Dimethyl ether carbonylation methyl acetate is a novelty
Path, the catalyst used in course of reaction is solid catalyst, corrosion-free easily separated, and can solve DME production capacity surpluses
Problem.
At present, it is mainly mordenite molecular sieve to study more, good catalytic activity catalyst.The skeleton of modenite
Along [001] direction there is 12 yuan of rings and 8 yuan of rings straight hole roads in structure, 8 membered ring channels are between 12 membered ring channels, edge
[010] there is also 8 yuan of rings straight hole roads in direction.12 yuan of rings apertures are oval, and size is 0.65nm × 0.70nm, [001] direction 8
Yuan of rings port size is 0.26nm × 0.57nm, and the yuan of rings port size of [010] direction side-seam pkt. 8 is 0.34nm × 0.48nm.Grind
Study carefully the dimethyl ether carbonylation reaction shown for molecular sieve catalytic, the activity of the acidic site in 8 membered ring channels is higher, and position
It is closely related in the acidic site in 12 membered ring channels and the inactivation of molecular sieve catalyst.Therefore, in order to improve the stabilization of catalyst
Property and methyl acetate selectivity, it is necessary to optionally weaken or eliminate work of the acidic site in reaction system in 12 yuan of rings
With.
Therefore, people take a variety of methods to realize this target.Conventional mainly has two kinds of pyridine adsorption and dealuminzation
Method.Pyridine adsorption agent is slowly desorbed the modenite of pre- Adsorption of Pyridine in use, is caused carbon deposition quantity gradually to increase, is made
The selectivity of modenite is deteriorated, lifetime, influences product quality.Using the side of acid or steam treatment modenite dealuminzation
Method, the poor selectivity of dealuminzation be present, and molecular sieve structure easily caves in and shortens the service life of modenite agent.
The content of the invention
It is an object of the invention to provide a kind of preparation method of the molecular sieve catalyst for carbonylation, it is possible to increase
Molecular sieve catalyst prepares the selectivity in methyl acetate reaction in dimethyl-carbonyl and extends the service life of molecular sieve.
Present invention also offers a kind of molecular sieve catalyst for carbonylation and its application.
In order to realize the above object the preparation method of the molecular sieve catalyst for carbonylation of the present invention is used
Technical scheme be：
A kind of preparation method of molecular sieve catalyst for carbonylation, comprises the following steps：
1) hydrogen type molecular sieve is immersed in metal salt solution and carries out ion exchange, be then calcined, obtain metal oxide modified
Molecular sieve；The hydrogen type molecular sieve is h-mordenite molecular sieve or Hydrogen ZSM-35 molecular sieve；The metal salt be La, Y,
At least one of Ca, Cu, Zn, Ga, Co, Ni, Zr, Fe salt；
2) the metal oxide modified molecular sieve obtained in step 1) is catalyzed to unsaturated hydrocarbons progress at 400~600 DEG C
Carburizing reagent, obtain pre- carbon deposition catalyst；A diameter of 0.5~the 0.75nm of molecular dynamics of the unsaturated hydrocarbons；
3) the pre- carbon deposition catalyst obtained in step 2) is subjected to pickling using non-oxidizing acid, produced.
The preparation method of the molecular sieve catalyst for carbonylation of the present invention, metal-modified mistake is carried out to molecular sieve
Metal ion can be preferentially adsorbed on acidic site in journey, be more easy to promote by the shape-selective principle in reactant duct unsaturated in macropore
The carburizing reagent of hydrocarbon so that the carbon of generation is mainly deposited in macropore, is finally carried out pickling and is removed the yuan of rings of molecular sieve catalyst 8
Metal oxide in duct, recover intrinsic Bronsted acidity position, improve the catalytic activity of molecular sieve catalyst.
The preparation method of the molecular sieve catalyst for carbonylation of the present invention, can not influence 8 membered ring channels
In the case of interior acidic site, the acidic site in large-size duct is eliminated, so as to improve catalyst in Dimethyl ether carbonylation system
For the selectivity in methyl acetate reaction and extend the service life of molecular sieve.
In step 1), the hydrogen type molecular sieve is after molecular screen primary powder is calcined, and is prepared by ammonia exchange process.It will divide
Son sieves former powder and carries out being calcined the template that can be removed in molecular screen primary powder.The temperature being calcined after ion exchange be 500~
550 DEG C, the time is 2~6h.
In step 1), the metal salt is La, Y, Ca, Cu, Zn, Ga, Co, Ni, Zr, Fe nitrate, sulfate, acetic acid
Salt any one or a few.The metal oxide supported amount of the metal oxide modified molecular sieve is 0.5~2.5% (matter
Measure fraction).
Step 2) is additionally included in the metal oxide modified molecular sieve progress to being obtained in step 1) before progress carburizing reagent
Activation.Metal oxide modified system with molecular sieve for preparing gets preferably direct catalysis carburizing reagent ready, then after being placed a period of time
Just need to carry out activation process to it before use, the moisture adsorbed during oxide modifying molecular sieve is placed can be removed and had
Machine impurity, improve reactivity worth.It is described activation be by metal oxide modified molecular sieve in activation phenomenon, at 400~600 DEG C
It is incubated 0.5~5h.The activation phenomenon is nitrogen, air, oxygen or helium.The reactor that the activation uses is anti-for fixed bed
Answer device, fluidized-bed reactor or moving-burden bed reactor.
In step 2), the unsaturated hydrocarbons is butylene, butadiene, amylene, cyclopentene, hexene, cyclohexene, benzene, toluene, two
Any one or a few in toluene.The pressure of the carburizing reagent is normal pressure.The quality of unsaturated hydrocarbons in carbonation reaction
Air speed is 0.5~15.0h-1.The reactor that the carburizing reagent uses is fixed bed reactors, fluidized-bed reactor or moving bed
Reactor.
Preferably, the mass space velocity of unsaturated hydrocarbons is 4.0~15.0h in carbonation reaction-1。
In step 2), in carbonation reaction, the conversion ratio of unsaturated hydrocarbons is less than after 5%, stops reaction.It can use
Stop the method stopping reaction that unsaturated hydrocarbons feeds and uses inert gas to catalyst purge cooling.The inert gas
For nitrogen or helium.
In step 3), the pickling is to carry out being mixed and stirred for 1~12h by non-oxidizing acid and pre- carbon deposition catalyst.Institute
State the material of non-oxidizing acid amount it is dense be 0.05~1.0mol/L.Sial of the non-oxidizing acid of low concentration to framework of molecular sieve
Concentration than influenceing little while higher non-oxidizing acid can improve the silica alumina ratio of framework of molecular sieve, so as to improve molecule
Stability of the sieve catalyst in dimethyl ether carbonylation reaction.
Preferably, the substance withdrawl syndrome of the non-oxidizing acid is 0.5~1.0mol/L.
The non-oxidizing acid is at least one of hydrochloric acid, acetic acid, sulfuric acid.The concentration of the sulfuric acid be 0.05~
0.5mol/L。
Technical scheme is used by the molecular sieve catalyst for carbonylation of the present invention：
A kind of molecular sieve catalyst for carbonylation obtained using above-mentioned preparation method.
Application of the molecular sieve catalyst for carbonylation of the present invention in terms of dimethyl ether carbonylation reaction is adopted
Technical scheme is：
A kind of above-mentioned application for the molecular sieve catalyst of carbonylation in terms of dimethyl ether carbonylation reaction.
Brief description of the drawings
Fig. 1 is the flow chart of the preparation method of the molecular sieve catalyst for carbonylation in embodiment.
Embodiment
Technical scheme is further described below in conjunction with embodiment.
Unsaturated hydrocarbons charging can be fed using pump in each embodiment or carrier gas is carried by the way of feeding, and be fed using carrier gas
When raw material can be heated using water-bath, and control feedstock vapor pressure to regulate and control the reaction of raw material by adjusting bath temperature
Air speed.
Si/Al=8.5 in the mordenite molecular sieve original powder used in embodiment；The ZSM-35 molecular sieve of use
Si/Al=7.5 in former powder.
Embodiment 1
The preparation method of the molecular sieve catalyst for carbonylation of the present embodiment, as shown in figure 1, including following step
Suddenly：
1) mordenite molecular sieve original powder is calcined, is then immersed in 1mol/L ammonium nitrate solutions and soaks 2h progress ammonia friendships
Change, be washed out, dry, repeat the step 3 time that ammonia is exchanged, washs, dried, then carry out roasting 4h at 550 DEG C, Hydrogen is made
Mordenite molecular sieve；
2) obtained h-mordenite molecular sieve in step 1) is immersed in the mixed solution of lanthanum nitrate and calcium nitrate and soaked
Steep 4h and carry out ion exchange, then filter, dry, then 4h is calcined at 500 DEG C, it is 0.5% (quality to obtain metal oxide supported amount
Fraction) metal oxide modified molecular sieve；The substance withdrawl syndrome of lanthanum nitrate is 1.0mol/L in the mixed solution, calcium nitrate
Substance withdrawl syndrome be 1.0mol/L；
3) obtained metal oxide modified molecular sieve in a certain amount of step 2) is taken to be placed in reactor, in the purging of nitrogen
Under be heated to 400 DEG C and be incubated 5h, then pass to isobutene temperature be 400 DEG C, normal pressure, mass space velocity 5.0h-1Condition
Under carry out catalysis carburizing reagent, when isobutene conversion ratio be less than 5% when, stop charging, and with nitrogen purging catalyst layer drop
Temperature, pre- carbon deposition catalyst is obtained, now the conversion ratio of isobutene is 4.2%；
4) pre- carbon deposition catalyst made from step 3) and concentration are mixed for 0.2mol/L hydrochloric acid, stirred at 50 DEG C
12h is mixed, then filters, wash, dry, produce.
The molecular sieve catalyst for carbonylation of the present embodiment is obtained using upper preparation method.
Embodiment 2
The preparation method of the molecular sieve catalyst for carbonylation of the present embodiment, comprises the following steps：
1) mordenite molecular sieve original powder is calcined, is then immersed in 1mol/L ammonium nitrate solutions and soaks 2h progress ammonia friendships
Change, be washed out, dry, repeat the step 3 time that ammonia is exchanged, washs, dried, then carry out roasting 4h at 550 DEG C, Hydrogen is made
Mordenite molecular sieve；
2) it is that 3mol/L copper sulphate is molten obtained h-mordenite molecular sieve in step 1) to be immersed into substance withdrawl syndrome
6h is soaked in liquid and carries out ion exchange, then filters, dry, then 4h is calcined at 550 DEG C, obtaining metal oxide supported amount is
2.5% (mass fraction) metal oxide modified molecular sieve；
3) obtained metal oxide modified molecular sieve in a certain amount of step 2) is taken to be placed in reactor, in the purging of air
Under be heated to 600 DEG C and be incubated 3h, be then cooled to 500 DEG C, it is 500 DEG C, often that iso-amylene is passed through after temperature stabilization in temperature
Pressure, mass space velocity 4.0h-1Under conditions of carry out catalysis carburizing reagent, when iso-amylene conversion ratio be less than 5% when, stop into
Material, and cooled with helium purge catalyst layer, pre- carbon deposition catalyst is obtained, now the conversion ratio of iso-amylene is 3.1%；
4) pre- carbon deposition catalyst made from step 3) and concentration are mixed for 0.3mol/L hydrochloric acid, stirred at 60 DEG C
8h is mixed, then filters, wash, dry, produce.
The molecular sieve catalyst for carbonylation of the present embodiment is obtained using upper preparation method.
Embodiment 3
The preparation method of the molecular sieve catalyst for carbonylation of the present embodiment, comprises the following steps：
1) mordenite molecular sieve original powder is calcined, is then immersed in 1mol/L ammonium nitrate solutions and soaks 2h progress ammonia friendships
Change, be washed out, dry, repeat the step 3 time that ammonia is exchanged, washs, dried, then carry out roasting 4h at 550 DEG C, Hydrogen is made
Mordenite molecular sieve；
2) it is 2.0mol/L zinc acetates obtained h-mordenite molecular sieve in step 1) to be immersed into substance withdrawl syndrome
10h is soaked in solution and carries out ion exchange, then filters, dry, then 6h is calcined at 500 DEG C, obtaining metal oxide supported amount is
1.5% (mass fraction) metal oxide modified molecular sieve；
3) obtained metal oxide modified molecular sieve in a certain amount of step 2) is taken to be placed in reactor, in the purging of oxygen
Under be heated to 500 DEG C and be incubated 4h, be then cooled to 450 DEG C, it is 450 DEG C, often that iso-amylene is passed through after temperature stabilization in temperature
Pressure, mass space velocity 4.5h-1Under conditions of carry out catalysis carburizing reagent, when iso-amylene conversion ratio be less than 5% when, stop into
Material, and cooled with helium purge catalyst layer, pre- carbon deposition catalyst is obtained, now the conversion ratio of iso-amylene is 4.8%；
4) pre- carbon deposition catalyst made from step 3) and concentration are mixed for 0.4mol/L hydrochloric acid, stirred at 60 DEG C
6h is mixed, then filters, wash, dry, produce.
The molecular sieve catalyst for carbonylation of the present embodiment is obtained using upper preparation method.
Embodiment 4
The preparation method of the molecular sieve catalyst for carbonylation of the present embodiment, comprises the following steps：
1) mordenite molecular sieve original powder is calcined, is then immersed in 1mol/L ammonium nitrate solutions and soaks 2h progress ammonia friendships
Change, be washed out, dry, repeat the step 3 time that ammonia is exchanged, washs, dried, then carry out roasting 4h at 550 DEG C, Hydrogen is made
Mordenite molecular sieve；
2) it is 1.5mol/L nickel nitrates obtained h-mordenite molecular sieve in step 1) to be immersed into substance withdrawl syndrome
12h is soaked in solution and carries out ion exchange, then filters, dry, then 2h is calcined at 550 DEG C, obtaining metal oxide supported amount is
1.0% (mass fraction) metal oxide modified molecular sieve；
3) obtained metal oxide modified molecular sieve in a certain amount of step 2) is taken to be placed in reactor, in the purging of helium
Under be heated to 600 DEG C and be incubated 2h, be then cooled to 550 DEG C, it is 550 DEG C, often that cyclohexene is passed through after temperature stabilization in temperature
Pressure, mass space velocity 10.0h-1Under conditions of carry out catalysis carburizing reagent, when cyclohexene conversion ratio be less than 5% when, stop into
Material, and cooled with helium purge catalyst layer, pre- carbon deposition catalyst is obtained, now the conversion ratio of cyclohexene is 3.2%；
4) pre- carbon deposition catalyst made from step 3) and concentration are mixed for 1.0mol/L acetic acid, stirred at 80 DEG C
5h is mixed, then filters, wash, dry, produce.
The molecular sieve catalyst for carbonylation of the present embodiment is obtained using upper preparation method.
Embodiment 5
The preparation method of the molecular sieve catalyst for carbonylation of the present embodiment, comprises the following steps：
1) ZSM-35 molecular sieve original powder is calcined, is then immersed in 1mol/L ammonium nitrate solutions and soaks 2h progress ammonia exchanges,
It is washed out, dries, repeats the step 3 time that ammonia is exchanged, washs, dried, then carry out roasting 4h at 550 DEG C, Hydrogen is made
ZSM-35 molecular sieve；
2) obtained Hydrogen ZSM-35 molecular sieve in step 1) is immersed in the mixed solution of ferric sulfate and yttrium nitrate and soaked
4h carries out ion exchange, then filters, dries, then is calcined 3h at 550 DEG C, obtains metal oxide supported amount as 2.4% (quality point
Number) metal oxide modified molecular sieve；The substance withdrawl syndrome of ferric sulfate is 3.0mol/L in the mixed solution, yttrium nitrate
Substance withdrawl syndrome is 1.0mol/L；
3) obtained metal oxide modified molecular sieve in a certain amount of step 2) is taken to be placed in reactor, in the purging of nitrogen
Under be heated to 600 DEG C and be incubated 2h, then pass to cyclopentene temperature be 600 DEG C, normal pressure, mass space velocity 5.0h-1Condition
Under carry out catalysis carburizing reagent, when cyclopentene conversion ratio be less than 5% when, stop charging, and with nitrogen purging catalyst layer drop
Temperature, pre- carbon deposition catalyst is obtained, now the conversion ratio of cyclopentene is 1.1%；
4) pre- carbon deposition catalyst made from step 3) and concentration are mixed for 0.1mol/L sulfuric acid, stirred at 40 DEG C
5h is mixed, then filters, wash, dry, produce.
The molecular sieve catalyst for carbonylation of the present embodiment is obtained using upper preparation method.
Embodiment 6
The preparation method of the molecular sieve catalyst for carbonylation of the present embodiment, comprises the following steps：
1) ZSM-35 molecular sieve original powder is calcined, is then immersed in 1mol/L ammonium nitrate solutions and soaks 2h progress ammonia exchanges,
It is washed out, dries, repeats the step 3 time that ammonia is exchanged, washs, dried, then carry out roasting 4h at 550 DEG C, Hydrogen is made
ZSM-35 molecular sieve；
2) it is that 1.0mol/L zirconium nitrates are molten obtained Hydrogen ZSM-35 molecular sieve in step 1) to be immersed into substance withdrawl syndrome
1h is soaked in liquid and carries out ion exchange, then filters, dry, then 4h is calcined at 500 DEG C, obtaining metal oxide supported amount is
0.5% (mass fraction) metal oxide modified molecular sieve；
3) obtained metal oxide modified molecular sieve in a certain amount of step 2) is taken to be placed in reactor, in the purging of air
Under be heated to 600 DEG C and be incubated 1h, then pass to paraxylene temperature be 600 DEG C, normal pressure, mass space velocity 15h-1Condition
Under carry out catalysis carburizing reagent, when the conversion ratio of paraxylene is less than 5%, stop charging, and with helium purge catalyst layer
Cooling, obtains pre- carbon deposition catalyst, and now the conversion ratio of paraxylene is 2.8%；
4) pre- carbon deposition catalyst made from step 3) and concentration are mixed for 0.2mol/L sulfuric acid, stirred at 30 DEG C
3h is mixed, then filters, wash, dry, produce.
The molecular sieve catalyst for carbonylation of the present embodiment is obtained using upper preparation method.
Embodiment 7
The preparation method of the molecular sieve catalyst for carbonylation of the present embodiment, comprises the following steps：
1) ZSM-35 molecular sieve original powder is calcined, is then immersed in 1mol/L ammonium nitrate solutions and soaks 2h progress ammonia exchanges,
It is washed out, dries, repeats the step 3 time that ammonia is exchanged, washs, dried, then carry out roasting 4h at 550 DEG C, Hydrogen is made
ZSM-35 molecular sieve；
2) it is that 1.5mol/L yttrium nitrates are molten obtained Hydrogen ZSM-35 molecular sieve in step 1) to be immersed into substance withdrawl syndrome
5h is soaked in liquid and carries out ion exchange, then filters, dry, then 4h is calcined at 550 DEG C, obtaining metal oxide supported amount is
0.9% (mass fraction) metal oxide modified molecular sieve；
3) obtained metal oxide modified molecular sieve in a certain amount of step 2) is taken to be placed in reactor, in the purging of air
Under be heated to 600 DEG C and be incubated 0.5h, then pass to paraxylene and butadiene (amount of the material of paraxylene and butadiene it
Than for 1:1) temperature be 600 DEG C, normal pressure, gross mass air speed be 8h-1Under conditions of carry out catalysis carburizing reagent, treat to diformazan
When the conversion ratio of benzene and butadiene is below 5%, stop charging, and cooled with helium purge catalyst layer, obtain pre- carbon distribution and urge
Agent, now the conversion ratio of paraxylene is 3.0%, and the conversion ratio of butadiene is 4.5%；
4) pre- carbon deposition catalyst made from step 3) and concentration are mixed for 0.5mol/L sulfuric acid, stirred at 30 DEG C
1h is mixed, then filters, wash, dry, produce.
The molecular sieve catalyst for carbonylation of the present embodiment is obtained using upper preparation method.
Embodiment 8
The molecular sieve catalyst for carbonylation of embodiment 1~7 is obtained into 40~60 mesh through tabletting, screening respectively
Particle, 1g is then respectively taken to be respectively charged into the pressurization stainless steel fixed bed reactors (internal diameter 8mm) continuously flowed, then using lazy
Property atmosphere activation after be cooled to 200 DEG C, after temperature stabilization, by the mixed gas of dimethyl ether, carbon monoxide and hydrogen in pressure
For 2.0MPa, gas volume air speed carries out reaction production methyl acetate under conditions of being 1500ml/g/h；Wherein hydrogen and
The total flow of dimethyl ether is 16.4ml/min, and the volume ratio of dimethyl ether, carbon monoxide and hydrogen is 5:35:60.Each molecular sieve is urged
The reactivity worth of agent is shown in Table 1.
The reactivity worth evaluation of the molecular sieve catalyst for carbonylation of the embodiment 1~7 of table 1
| Embodiment | Dimethyl ether conversion ratea(%) | Methyl acetate selectivityb(%) | Life-spanc(h) |
| 1 | 39.2 | 96.5 | 15.3 |
| 2 | 38.6 | 98.6 | 13.4 |
| 3 | 35.3 | 99.5 | 14.6 |
| 4 | 37.6 | 98.3 | 12.4 |
| 5 | 38.2 | 95.3 | 16.1 |
| 6 | 40.1 | 94.8 | 17.4 |
| 7 | 42.6 | 97.8 | 15.5 |
Note：a：Maximum conversion in course of reaction；b：In course of reaction during maximum conversion methyl acetate selectivity；c：
Conversion ratio is reduced to the time used in maximum conversion half.
Comparative example
Catalyst of the comparative example using the mordenite molecular sieve without any processing as production methyl acetate, produces acetic acid
The technique and technological parameter of methyl esters are shown in Table 2 with embodiment 8, the reactivity worth of the catalyst of comparative example completely.
The reactivity worth evaluation of the catalyst of the comparative example of table 2
| Dimethyl ether conversion ratea(%) | Methyl acetate selectivityb(%) | Life-spanc(h) | |
| Comparative example | 48.1 | 93.5 | 8.5 |
Note：a：Maximum conversion in course of reaction；b：In course of reaction during maximum conversion methyl acetate selectivity；c：
Conversion ratio is reduced to the time used in maximum conversion half.
From the data in Tables 1 and 2, the molecular sieve catalyst for carbonylation of the invention can improve pair
The selectivity of methyl acetate, and can significantly extend the life-span of catalyst.
Claims (10)
- A kind of 1. preparation method of molecular sieve catalyst for carbonylation, it is characterised in that：Comprise the following steps：1) hydrogen type molecular sieve is immersed in metal salt solution and carries out ion exchange, be then calcined, obtain metal oxide modified molecule Sieve；The hydrogen type molecular sieve is h-mordenite molecular sieve or Hydrogen ZSM-35 molecular sieve；The metal salt be La, Y, Ca, At least one of Cu, Zn, Ga, Co, Ni, Zr, Fe salt；2) the metal oxide modified molecular sieve obtained in step 1) is catalyzed into unsaturated hydrocarbons at 400~600 DEG C to be carbonized Reaction, obtains pre- carbon deposition catalyst；A diameter of 0.5~the 0.75nm of molecular dynamics of the unsaturated hydrocarbons；3) the pre- carbon deposition catalyst obtained in step 2) is subjected to pickling using non-oxidizing acid, produced.
- 2. the preparation method of the molecular sieve catalyst according to claim 1 for carbonylation, it is characterised in that：Step It is rapid 1) in, the hydrogen type molecular sieve is after molecular screen primary powder is calcined, and is prepared by ammonia exchange process.
- 3. the preparation method of the molecular sieve catalyst according to claim 1 for carbonylation, it is characterised in that：Step It is rapid 2) be additionally included in carry out carburizing reagent before the obtained metal oxide modified molecular sieve in step 1) is activated；It is described Activation is that metal oxide modified molecular sieve is incubated into 0.5~5h in activation phenomenon, at 400~600 DEG C.
- 4. the preparation method of the molecular sieve catalyst according to claim 3 for carbonylation, it is characterised in that：Institute It is nitrogen, air, oxygen or helium to state activation phenomenon.
- 5. the preparation method of the molecular sieve catalyst according to claim 1 for carbonylation, it is characterised in that：Step It is rapid 2) in, the unsaturated hydrocarbons is butylene, butadiene, amylene, cyclopentene, hexene, cyclohexene, appointing in benzene,toluene,xylene Meaning is one or more of.
- 6. the preparation method of the molecular sieve catalyst according to claim 1 for carbonylation, it is characterised in that：Step It is rapid 2) in, the mass space velocity of unsaturated hydrocarbons is 0.5~15.0h in carbonation reaction-1。
- 7. the preparation method of the molecular sieve catalyst according to claim 1 for carbonylation, it is characterised in that：Step It is rapid 2) in, in carbonation reaction, the conversion ratio of unsaturated hydrocarbons is less than after 5%, stops reaction.
- 8. the preparation method of the molecular sieve catalyst according to claim 1 for carbonylation, it is characterised in that：Step It is rapid 3) in, the pickling is to carry out being mixed and stirred for 1~12h by non-oxidizing acid and pre- carbon deposition catalyst.
- A kind of 9. molecular sieve catalyst for carbonylation obtained using preparation method as claimed in claim 1.
- 10. a kind of molecular sieve catalyst as claimed in claim 9 for carbonylation is in dimethyl ether carbonylation reaction side The application in face.
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| CN113200554A (en) * | 2021-05-07 | 2021-08-03 | 中国矿业大学 | Nano mordenite molecular sieve and preparation method and application thereof |
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