CN105315120B - A kind of method that benzene reacts with methanol alkylation - Google Patents
A kind of method that benzene reacts with methanol alkylation Download PDFInfo
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to a kind of benzene and the method for methanol alkylation reaction, the method includes：In the presence of the catalyst containing the molecular sieves of H types IM 5, by benzene and methyl alcohol haptoreaction, wherein, the SiO of the molecular sieves of H types IM 52/Al2O3Mol ratio is 55 100.Significantly higher benzene conversion ratio and dimethylbenzene selective can be obtained according to the method that benzene of the present invention and methanol alkylation react, and can substantially reduce C5 ‑Low-carbon (LC) hydrocarbon-selective, reduces the side reaction of methyl alcohol.
Description
Technical field
The present invention relates to a kind of benzene and the method for methanol alkylation reaction.
Background technology
Benzene is a kind of high reaction of industrial application value with methanol alkylation reaction, and the method can be closed by primary first-order equation
Into application value toluene and dimethylbenzene higher, especially highly important industrial basic organic paraxylene, and should
Benzene feedstock and the methyl alcohol source of reaction are wide, cheap.So far, benzene is very few with the research of methanol alkylation, but domestic and international land
It is continuous to have started to carry out the research to the reaction.
After since the seventies in last century, Mobile companies in the U.S. develop ZSM-5 zeolite, because it is to alkylation, isomery
The reactions such as change, phenyl ring methylate, selective cracking process all show excellent catalytic performance, are paid attention to extensively, and people are also by benzene first
The catalysis material of alcohol phenyl ring alkylated reaction is focused on to be placed on ZSM-5 molecular sieve and ZSM-5 molecular sieve is modified
Treatment.ZSM-5 molecular sieve is the pore canal system being made up of 10 membered oxygen rings, with medium sized aperture and aperture.(the stones such as Lu Lu
Oily journal, 2012,2：111-115) report the 6%MgO/ multi-stage porous ZSM-5 molecules that will possess micropore and mesoporous two kinds of ducts
Sieve the conversion ratio and toluene and diformazan more than 90% of the benzene that up to 55% can be obtained in being reacted for benzene and methanol alkylation
The selectivity of benzene, compared with common ZSM-5 molecular sieve, the conversion ratio of the benzene that multi-stage porous ZSM-5 molecular sieve is obtained improves about
9%, the selectivity of toluene and dimethylbenzene improves about 3%.
With the progress of molecular sieve research work, some novel molecular sieves are also progressively used for benzene and methanol alkylation by people
In reaction.MCM-22 molecular sieves are synthesized first by Mobile companies in nineteen ninety.Due to unique structural property, with MCM-
22 is the field table such as alkene and aromatic hydrocarbons, catalytic cracking, isomerisation of olefin, hydro carbons alkylation in alkane transformations for the catalyst of carrier
Good catalytic performance is revealed, according to structure and the difference of preparation method, has found up to the present and successively and synthesize
The equally lamellar zeolite with MWW structures such as MCM-36, MCM-49, MCM-56, ITQ-1, ITQ-2.They all with send out at first
Existing MCM-22 has certain affiliation, and MCM-22 family molecular sieves are summarized as together with MCM-22.CN102600887A
Report using on Hydrogen MCM-22 molecular sieves supported alkaline earth, thulium technical scheme, preferably solve with
Methanol alkylation utilization rate is low in catalyst practical application toward document, benzene conversion ratio is not high and dimethylbenzene selective is low
Shortcoming.MCM-56 belongs to the molecular sieve of MWW structures, and 10 membered ring channels and 12 yuan of rings holes with uniqueness, excellent hydro-thermal are steady
Qualitative and special acid site distribution, is a kind of new catalysis material, and CN102101818A is reported, with HMCM-56 points
Son sieve be carrier, carried metal Mo or Ni, its mass content is respectively with MoO3Or NiO meters, its load quality is 3-15%, toluene
With selectivity >=89% of dimethylbenzene；Conversion per pass >=45% of benzene.The conversion ratio of the selectivity and benzene of toluene and dimethylbenzene
Still it is undesirable, it is necessary to improve.
IM-5 molecular sieves are synthesized first by Suk Bong Hong et al. (US6136290).The molecular sieve is two dimension ten
The pore passage structure of yuan of rings, there is larger-size limited duct on third dimension direction, its pore passage structure has similar to ZSM-5 molecular sieve
Also there is a cagelike structure for 12 yuan of rings in part, the molecular sieve, have difference again compared with ZSM-5.IM-5 molecular sieves exist
Good catalytic performance has all been shown in many reactions.United States Patent (USP) US6344135 and US6667267 are reported containing IM-5
Application of the catalyst in being hydrocracked, its conversion ratio that can improve hydrocracking reaction, while improving the yield of gasoline.It is beautiful
State patent US6007698 reports application of the catalyst containing IM-5 in catalytic cracking, and the catalyst can effectively improve reaction
Conversion ratio, while improve propylene yield.The IM-5 catalyst containing P Modification is applied in catalytic cracking simultaneously, can improve product
The yield of gasoline in thing, can also improve the selectivity (US6306286) of propylene.CN1140612A reports urging containing zeolite IM -5
Agent can be effectively improved alkane material flow point.IM-5 molecular sieves can have preferable catalytic performance in numerous reactions, mainly
Have benefited from its pore passage structure got by oneself, and acid distribution, while having heat and hydrothermal stability well.However, existing text
To offer do not report and IM-5 molecular sieves are applied in benzene and methanol alkylation reaction.
The content of the invention
It is an object of the invention to provide a kind of benzene and the method for methanol alkylation reaction, the method used catalyst activity
Height, arenes selectivity is good.
The invention provides a kind of benzene and the method for methanol alkylation reaction, the method includes：Containing H type IM-5 molecules
In the presence of the catalyst of sieve, by benzene and methyl alcohol haptoreaction, wherein, the SiO of the H types IM-5 molecular sieves2/Al2O3Mol ratio
It is 55-100.
In the method for the benzene and the methanol alkylation reaction that the present invention is provided, by using containing H type IM-5 molecules
The catalyst of sieve, in the case where ensuring that benzene conversion ratio is higher, improves the selectivity of dimethylbenzene, at the same methanol conversion compared with
Height, the C in product5 -Low-carbon (LC) hydrocarbon content is relatively low, reduces the side reaction of methyl alcohol.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that described herein specific
Implementation method is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The method that the benzene that the present invention is provided reacts with methanol alkylation includes：Containing H type IM-5 molecular sieves (HIM-
5 molecular sieves) catalyst in the presence of, by benzene and methyl alcohol haptoreaction, wherein, the SiO of the H types IM-5 molecular sieves2/Al2O3
Mol ratio is 55-100, preferably 60-75.
In method of the benzene for providing of the invention with methanol alkylation reaction, the catalyst can also contain bonding
Agent, and in the catalyst, on the basis of the gross weight of the catalyst, the content of the H types IM-5 molecular sieves can be
20-90 weight %, preferably 40-80 weight %；The content of the binding agent can be 10-80 weight %, preferably 20-60 weights
Amount %.
In the present invention, the binding agent can be various binding agents commonly used in the art, preferably silica.
In method of the benzene that the present invention is provided with methanol alkylation reaction, H types IM-5 points in the catalyst or catalyst
Son sieve is preferably through hydro-thermal process.It is further preferred that the condition of the hydro-thermal process includes：Temperature is 400-580 DEG C, more excellent
Elect 460-500 DEG C as；Time is preferably 4-8 hours.During hydro-thermal process, water vapour can be with by the mass space velocity of mol sieve beds
It is 1-5h-1, preferably 1.5-2.5h-1。
The first implementation method of the invention, the catalyst used in the method that the benzene reacts with methanol alkylation
It is H type IM-5 molecular sieves.The preparation method of the H types IM-5 molecular sieves can include：By Na type IM-5 molecular sieves, (NaIM-5 divides
Son sieve) ammonium exchange is carried out, then dry and be calcined.
In the preparation process of the H types IM-5 molecular sieves, the process that the ammonium is exchanged can include：By Na types IM-5 points
Son sieve is contacted with ammonium nitrate solution.In the ammonium exchange process, the solid-to-liquid ratio (g/ of Na type IM-5 molecular sieves and ammonium nitrate solution
Ml can be) 1：5-10.The concentration of ammonium nitrate solution used can be 0.1-0.5mol/L (i.e. 0.1-0.5N).In preferred feelings
Under condition, the ammonium is exchanged to be carried out repeatedly, for example, can be 2-4 times, most preferably 3 times.And, each ammonium clearing house carry out when
Between can be 0.5-5 hours, preferably 1-3 hours.
In the preparation process of the H types IM-5 molecular sieves, drying process can be carried out at 90-120 DEG C.
In the preparation process of the H types IM-5 molecular sieves, the implementation condition of roasting process can include：Sintering temperature is
500-550 DEG C, roasting time is 3-7 hours.
Second implementation method of the invention, the catalyst used in the method that the benzene reacts with methanol alkylation
It is by the H type IM-5 molecular sieves of hydro-thermal process, preferably by the H types IM-5 of hydro-thermal process 4-8 hours at 400-500 DEG C
Molecular sieve.The preparation method of the H type IM-5 molecular sieves by hydro-thermal process can include：H types are prepared according to preceding method
IM-5 molecular sieves, then carry out hydro-thermal process.
The third implementation method of the invention, the catalyst used in the method that the benzene reacts with methanol alkylation
It is the catalyst containing H type IM-5 molecular sieves and binding agent.The preparation method of the catalyst can include：According to preceding method system
Standby H type IM-5 molecular sieves, then mix the H type IM-5 molecular sieves with binding agent, then carry out roller forming and roasting, so that
The catalyst of shaping is obtained.The implementation condition of roasting process herein can include：Sintering temperature is 500-600 DEG C, during roasting
Between be 3-7 hours.
In a kind of specific embodiment, the preparation method of the catalyst containing H type IM-5 molecular sieves and binding agent includes：
By the ammonium nitrate solution of NaIM-5 molecular sieves and 0.1-0.5N with solid-to-liquid ratio (g/ml) 1：The ratio of 5-10, exchanges in 80 DEG C of stirrings
3 times, two hours every time, filtering, the drying at 90-120 DEG C were calcined 5 hours at 500-550 DEG C, and HIM-5 molecular sieves are obtained；
The binding agent silica of the HIM-5 molecular sieves of 40-80 weight % and 20-60 weight % is sufficiently mixed uniformly, roller forming,
Temperature programming is calcined 5 hours to 540 DEG C, so as to the catalyst of shaping is obtained.
4th kind of implementation method of the invention, the catalyst used in the method that the benzene reacts with methanol alkylation
It is to contain the H type IM-5 molecular sieves and the catalyst of binding agent by hydro-thermal process.The preparation method of the catalyst can include：
According to preceding method prepare by hydro-thermal process H type IM-5 molecular sieves, then by this by hydro-thermal process H type IM-5 molecules
Sieve mixes with binding agent, then carries out roller forming and roasting, so as to the catalyst of shaping is obtained.The reality of roasting process herein
The condition of applying can include：Sintering temperature is 500-600 DEG C, and roasting time is 3-7 hours.
In a kind of specific embodiment, contain H type IM-5 molecular sieves and the catalyst of binding agent by hydro-thermal process
Preparation method include：By the ammonium nitrate solution of NaIM-5 molecular sieves and 0.1-0.5N with solid-to-liquid ratio (g/ml) 1：The ratio of 5-10
Example, stirs at 80 DEG C and exchanges 3 times, and two hours every time, filtering, the drying at 90-120 DEG C were calcined 5 small at 500-550 DEG C
When, HIM-5 molecular sieves are obtained；By HIM-5 molecular sieves, (steam quality air speed is 1h at 460-500 DEG C-1) hydro-thermal process 4-
8h, then will be sufficiently mixed uniformly by the binding agent silica of the HIM-5 molecular sieves of hydro-thermal process and 20-60 weight %,
Roller forming, temperature programming is calcined 5 hours to 540 DEG C, so as to the catalyst of shaping is obtained.
In benzene of the present invention and the method for methanol alkylation reaction, benzene can be wrapped with the catalytic condition of methyl alcohol
Include：Reaction temperature is 300-500 DEG C, and reaction pressure is 0.1-2MPa.In the present invention, pressure refers to absolute pressure.Benzene and first
The mol ratio of the consumption of alcohol can be 0.3-2：1.
In benzene of the present invention and the method for methanol alkylation reaction, benzene can be various normal with methyl alcohol haptoreaction
Carried out in the reactor of rule, for example, can be carried out in fixed bed reactors.When benzene and methyl alcohol haptoreaction are in fixed bed reaction
When being carried out in device, benzene can be 1-15h with the weight (hourly) space velocity (WHSV) of the mixed material of methyl alcohol-1.Raw material can be without carrying in course of reaction
Gas is carried, if being carried with carrier gas, carrier gas can be 15 with the mol ratio of mixed material：Less than 1, preferably 5-15：1.It is described
Carrier gas can be nitrogen, water vapour and C1-C3Hydrocarbon at least one.
The invention will be further described by the following examples.
Preparation example 1
By NaIM-5 molecular sieves and 0.5N ammonium nitrate solutions with solid-to-liquid ratio be 1：10 ratio, carries out 3 ammoniums at 80 DEG C
Ion exchange, every time 2 hours.Then, molecular sieve filtration is gone out, washing, 90 DEG C drying, 540 DEG C be calcined 5 hours, be obtained HIM-5
Molecular sieve, the Na of the HIM-5 molecular sieves2O content is less than 0.1 weight %, SiO2/Al2O3Mol ratio for 62, calcination loss
8%.The HIM-5 molecular sieves are designated as catalyst A.
Preparation example 2
Method according to preparation example 1 prepares HIM-5 molecular sieves, unlike, the SiO of IM-5 molecular sieves2/Al2O3Mole
Than being 68, obtained HIM-5 molecular sieves are designated as catalyst B.
Preparation example 3
Method according to preparation example 1 prepares HIM-5 molecular sieves, unlike, IM-5 molecular sieves SiO2/Al2O3Mol ratio
It is 75, obtained HIM-5 molecular sieves are designated as catalyst C.
Preparation example 4
Prepare the catalyst containing 80 weight % molecular sieves
Catalyst C is weighed into 750g, adds 420g Ludox (silica quality percentage 40%) to be sufficiently mixed uniformly,
Roller forming, temperature programming is calcined 5 hours to 540 DEG C, and shaping HIM-5 catalyst C4 is obtained.
Preparation example 5
Prepare the catalyst containing 70 weight % molecular sieves
Method according to preparation example 4 prepares catalyst, unlike, 740g Ludox is added, shaping HIM-5 catalysis is obtained
Agent C1.
Preparation example 6
Prepare the catalyst containing 60 weight % molecular sieves
Method according to preparation example 4 prepares catalyst, unlike, 1150g Ludox is added, shaping HIM-5 is obtained and urges
Agent C2.
Preparation example 7
Prepare by the HIM-5 molecular sieves of hydro-thermal process
Catalyst C is weighed into 800g, under the conditions of 500 DEG C, hydro-thermal process 4h, the air speed that water vapour passes through mol sieve beds
It is 2h-1, 9h then is dried at 90 DEG C, catalyst Ch1 is obtained.
Preparation example 8
Prepare by the HIM-5 molecular sieves of hydro-thermal process
Catalyst C is weighed into 800g, under the conditions of 460 DEG C, hydro-thermal process 6h, the air speed that water vapour passes through mol sieve beds
It is 2h-1, 9h then is dried at 90 DEG C, catalyst Ch2 is obtained.
Preparation example 9
Prepare by the HIM-5 molecular sieves of hydro-thermal process
Method according to preparation example 7 prepares catalyst, unlike, hydro-thermal process is carried out at 600 DEG C, catalyst is obtained
Ch3。
Preparation example 10
Prepare containing 70 weight % molecular sieves and by the HIM-5 molecular sieves of hydro-thermal process
Catalyst Ch1 is weighed into 750g, adds 740g Ludox (silica quality percentage 40%) to be sufficiently mixed
Even, roller forming, temperature programming is calcined 5 hours to 540 DEG C, and shaping HIM-5 catalyst Ch11 is obtained.
Preparation example 11
Prepare containing 70 weight % molecular sieves and by the HIM-5 molecular sieves of hydro-thermal process
Method according to preparation example 10 prepares catalyst, unlike, replace catalyst Ch1 with catalyst Ch3, it is obtained and urges
Agent Ch31.
Prepare reference example 1
Method according to preparation example 1 prepares HIM-5 molecular sieves, unlike, the SiO of IM-5 molecular sieves2/Al2O3Mole
Than being 47, obtained HIM-5 molecular sieves are designated as catalyst D.
Prepare reference example 2
Using SiO2/Al2O3Mol ratio be 60 NaZSM-5 molecular sieves, HZSM-5 point is prepared as described in Example 1
Son sieve, is designated as catalyst E.
Embodiment 1-11 and comparative example 1-2
On fixed bed reaction evaluating apparatus by preparation example 1-11 and prepare reference example 1-2 catalyst be used for benzene and methyl alcohol
Alkylated reaction, investigates reactivity and selectivity.Catalyst filling amount 2g, reaction raw materials (mol ratio) benzene：Methyl alcohol=1：1,
Reaction temperature is 440 DEG C, and reaction pressure is 0.5MPa, and weight (hourly) space velocity (WHSV) is 4h-1, carrier gas N2It is 10 with mixed material mol ratio.Instead
Answer result as shown in table 1.
Benzene conversion ratio=((entering reactor content benzene mole number-reactor outlet material benzene mole number)/enter reactor content
Benzene mole number) × 100%
Methylbenzene selective=(molal quantity of reactor outlet material toluene/(reactor outlet aromatic hydrocarbons material total mole number))
× 100%
Dimethylbenzene selective=(the molal quantity of reactor outlet material dimethylbenzene/(reactor outlet aromatic hydrocarbons material total moles
Number)) × 100%
C5 -Selectivity=(reactor outlet material C5 -Molal quantity/(reactor outlet material (do not include water) total moles
Number)) × 100%
Table 1
The method reacted according to benzene of the present invention and methanol alkylation can be seen that by above-described embodiment and comparative example
Significantly higher benzene conversion ratio and dimethylbenzene selective can be obtained, and can substantially reduce C5 -Low-carbon (LC) hydrocarbon-selective, is reduced
The side reaction of methyl alcohol.
Claims (12)
1. a kind of method that benzene reacts with methanol alkylation, the method includes：In depositing for the catalyst containing H type IM-5 molecular sieves
Under, by benzene and methyl alcohol haptoreaction, wherein, the SiO of the H types IM-5 molecular sieves2/Al2O3Mol ratio is 55-100, described
By hydro-thermal process, the condition of the hydro-thermal process includes H type IM-5 molecular sieves in catalyst or catalyst：Temperature is 400-
500 DEG C, the time is 4-8 hours.
2. method according to claim 1, wherein, the SiO of the H types IM-5 molecular sieves2/Al2O3Mol ratio is 60-75.
3. method according to claim 1 and 2, wherein, the catalyst also contains binding agent, and in the catalyst
In, on the basis of the gross weight of the catalyst, the content of the H types IM-5 molecular sieves is 20-90 weight %, the binding agent
Content be 10-80 weight %.
4. method according to claim 3, wherein, in the catalyst, on the basis of the gross weight of the catalyst,
The content of the H types IM-5 molecular sieves is 40-80 weight %；The content of the binding agent is 20-60 weight %.
5. method according to claim 3, wherein, the binding agent is silica.
6. method according to claim 4, wherein, the binding agent is silica.
7. the method according to any one in claim 1,2 and 4-6, wherein, the catalytic condition includes：Instead
Answer temperature for 300-500 DEG C, reaction pressure is 0.1-2MPa.
8. method according to claim 3, wherein, the catalytic condition includes：Reaction temperature is 300-500
DEG C, reaction pressure is 0.1-2MPa.
9. the method according to any one in claim 1,2 and 4-6, wherein, benzene is 0.3-2 with the mol ratio of methyl alcohol：
1。
10. method according to claim 3, wherein, benzene is 0.3-2 with the mol ratio of methyl alcohol：1.
11. method according to any one in claim 1,2 and 4-6, wherein, the haptoreaction benzene is mixed with methyl alcohol
The weight (hourly) space velocity (WHSV) for closing raw material is 1-15h-1, carrier gas is 0-15 with the mol ratio of mixed material：1.
12. methods according to claim 3, wherein, the weight (hourly) space velocity (WHSV) of the mixed material of the haptoreaction benzene and methyl alcohol
It is 1-15h-1, carrier gas is 0-15 with the mol ratio of mixed material：1.
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