CN103120949A - Methylbenzene methylation catalyst for increasing production of o-xylene and p-xylene and preparation method thereof - Google Patents

Methylbenzene methylation catalyst for increasing production of o-xylene and p-xylene and preparation method thereof Download PDF

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CN103120949A
CN103120949A CN2011103699917A CN201110369991A CN103120949A CN 103120949 A CN103120949 A CN 103120949A CN 2011103699917 A CN2011103699917 A CN 2011103699917A CN 201110369991 A CN201110369991 A CN 201110369991A CN 103120949 A CN103120949 A CN 103120949A
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xylene
paraxylene
catalyst
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modenite
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祁晓岚
孔德金
李晓韬
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The invention relates to a methylbenzene methylation catalyst for increasing production of o-xylene and p-xylene and a preparation method thereof, and is mainly used for solving the problems that in the prior art, the methylbenzene methylation catalyst only generates dimethylbenzene products in balanced distribution, and selectivity of o-xylene and p-xylene is lower. The catalyst comprises the components in parts by weight as follows: a) 5-95 parts of hydrogen mordenite (NaHMor) containing 0.8-2.8% of sodium ions; and b) 95-5 parts of bonder. The problems are better solved by adopting the technical scheme, and the catalyst can be applied to industrial production of o-xylene and p-xylene.

Description

The toluene methylation Catalysts and its preparation method of Increasing o-Xylene Output and paraxylene
Technical field
The present invention relates to the toluene methylation Catalysts and its preparation method of a kind of Increasing o-Xylene Output and paraxylene.
Background technology
Ortho-xylene is important chemical intermediate, mainly for the production of phthalic anhydride (being commonly called as phthalic anhydride).Phthalic anhydride is mainly used in the production of plasticizer and alkyd resins, unsaturated-resin, PEPA, polyester resin, also can be used for the intermediate of asccharin, pigment, dyestuff, medicine, pesticide producing.Continuous expansion along with the application of phthalic anhydride downstream product, particularly along with the development of Building Trade in China and traffic, electronics, aircraft industry, the extensive use of anti-corrosion material, a large amount of uses of unsaturated polyester resin and alkyd resins, market also presents its raw material ortho-xylene demand and increases progressively trend.
At present, the production capacity of domestic ortho-xylene can not be met the need of market far away, although in Technologies in Petrochemical Industry ortho-xylene manufacturer expand can comprehensively, but still can not meet the need of market, ortho-xylene still needs a large amount of imports, and import volume presents growth trend, and price is high, the import total amount reached 67.3 ten thousand tons in 2009, and unit price also increases to 9400-9500 unit/t at the beginning of 2011 by 5950 yuan/t at the beginning of 2004.
At present, the source of ortho-xylene mainly contains: 1. coal tar is mainly the accessory substance of coal industry and metallurgical industry.2. catalytic reforming.3. drippolene, the co-product of liquid material when preparing ethylene by steam cracking.4. toluene disproportionation and transalkylation.
In several ortho-xylene production methods, take with the paraxylene joint production process as best, the technique that adopts aromatic hydrocarbons separation and isomerization, disproportionation to unite was first separated ortho-xylene with rectification method before p-xylene separation.This method is two tower operations, and the first tower is realized ortho-xylene and other C8 isomer separation.Generate oil as raw material take catalytic reformate, drippolene and disproportionation, the Joint Production ortho-xylene is also the common method of producing ortho-xylene abroad.Benzene, toluene, mixed xylenes and paraxylene all can be produced simultaneously.Production procedure is flexible, can adjust product proportion according to the market demand, and resource fully and is reasonably utilized.
CN 1752057A produces mixed xylenes take benzene, toluene and carbon nine and above aromatic hydrocarbons thereof as raw material, first separate respectively adjacent, paraxylene, unreacted raw material circulation enters technique unit, when having solved the production ortho-xylene that exists in aromatic hydrocarbons transalkylation technology in the past in a large amount of benzene of by-product, raw material carbon nine and above heavy virtue thereof through the low problem of content and obtained higher neighbour, the paraxylene of purity, but the related one way distribution of reaction products of patent is not broken thermodynamical equilibrium, thus this patent be only to a certain extent raising its production capacity.
Paraxylene is also a kind of important Organic Chemicals, is mainly used in synthetic terephthalic acid (TPA) or dimethyl terephthalate (DMT), in fields such as polyester fiber, medicine, agricultural chemicals, dye well solvents, purposes is extremely widely arranged all.At present, it is raw material that mixed xylenes is mainly adopted in paraxylene production, produce by isomerization, adsorbing separation or Crystallization Separation, control owing to being subjected to thermodynamical equilibrium, paraxylene content in mixed xylenes only accounts for 24% left and right, in technical process, the Matter Transfer treating capacity is large, and equipment is huge, and operating cost is high.Also can adopt selective disproportionation of toluene technique, can generate the high concentration paraxylene, but toluene conversion is only 30%, solid circulating rate is also larger.
Development along with the C1 chemistry, the output of methyl alcohol increases, cost, if can directly synthesize the paraxylene of high concentration by toluene and methanol alkylation cheap and easy to get reaction, can reduce and separate and isomerized workload, economic benefit is considerable, thereby the research that utilizes alkylation of toluene methanol to select to generate paraxylene has caused people's very big interest.The alkylation of toluene methanol reaction can change into toluene the higher high concentration paraxylene of using value, has reduced and has separated and isomerized workload, and its economic benefit is with considerable.
Also not having in the world at present large-scale alkylation of toluene methanol reaction commodity production device to come out, is mainly whether the economic benefit of this class device will depend on supporting with large-scale methanol device.The focus that people pay close attention to is to react the preparation paraxylene by methylbenzene methanol shape selective alkylation to molecular sieve (being mainly ZSM-5 molecular sieve) modification, existing document has been done and has been summarized (Ge Xin etc., " Chinese Journal of Inorganic Chemistry ", 2001,17 (1): 17-26; Cao Dean, " Chemical Reaction Engineering and technique ", 2007,23 (4): 359-364).Also there is the problem of complicated, the easy coking deactivation of catalyst preparation process.And molecular sieve is not carried out modification, and can only obtain the mixed xylenes of thermodynamical equilibrium, wherein paraxylene accounts for 24% left and right, ortho-xylene accounts for 22% left and right, and the less meta-xylene of purposes accounts for 54%, and follow-up isomerization, separation of material circular treatment amount are large, energy consumption is high, and the easy coking deactivation of catalyst.
In recent years, also disclose both at home and abroad many take the patent of paraxylene as the purpose product.Patent CN 1762593A, US4067920, US 4011276, in US 5367099 and US 5607888, modification to the ZSM-5 molecular sieve structure has been proposed, namely reduce port size and shielding outer surface acidity active sites, prepare selective toluene disproportionation or methylation catalyst, above-mentioned patent is all to improve Selectivity for paraxylene as the purpose product, exist loaded down with trivial details, the used organosilicon modifier price of processing step high, complex structure or consumption are many, solvent for use is expensive, perhaps need add the parts that have much room for improvement such as precious metal in catalyst.
Zeolite molecular sieve has uniform composition and regular structure, and conventional zeolite molecular sieve (aluminosilicate zeolite molecular sieve) is the hydrated aluminosilicate crystal, has uniform aperture, by SiO 4And AlO 4Tetrahedron (is referred to as TO 4Tetrahedron) sharing oxygen atom is the basic skeleton structure unit, forms the crystal structure of shortrange order and long-range order.By SiO 4Tetrahedron and AlO 4The aluminosilicate zeolite molecular sieve that tetrahedron consists of has the anion frame structure, and the skeleton negative electrical charge is by extra cation balance.For synthetic zeolite, these cations are all sodium ions usually.These sodium ions can carry out reversible exchange with other cations, after exchange, the electrostatic field of crystals is changed, thereby change its performance, its change degree is difference with the difference of cationic property and exchange degree, after adopting ammonium salt solution to carry out ion-exchange to sodium type molecular sieve, molecular sieve just changes the ammonium type into, pass through again roasting, just change hydrogen type molecular sieve into, become solid acid.The zeolite molecular sieve that is typically used as acid catalyst is all hydrogen type molecular sieve, and its sodium content is less than 0.02%.
Summary of the invention
One of technical problem to be solved by this invention is to exist toluene methylation catalyst used can only be balanced the dimethylbenzene product of distribution in the past alkylation of toluene methanol technology, the problem that ortho-xylene and Selectivity for paraxylene are on the low side provides a kind of new Increasing o-Xylene Output and the toluene methylation catalyst of paraxylene.This catalyst is used for the toluene methylation reaction, has advantages of that ortho-xylene and Selectivity for paraxylene are high; Two of technical problem to be solved by this invention is to provide a kind of preparation method of the catalyst corresponding with one of technical solution problem.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the toluene methylation catalyst of a kind of Increasing o-Xylene Output and paraxylene comprises following component in parts by weight: a) h-mordenite that contains sodium ion 0.08-2.8% weight (NaHMor) of 5～95 parts; B) binding agent of 95～5 parts.
In technique scheme, the mol ratio of silica and aluminium oxide [n (SiO in modenite 2)/n (Al 2O 3), be called for short silica alumina ratio, as follows] preferable range is 8-80.The binding agent preferred version is selected from least a in Ludox, boehmite or aluminium oxide.The preferable range that h-mordenite (NaHMor) contains sodium ion is 0.10-2.0% weight.The organic acid preferred version is selected from least a in citric acid, oxalic acid or tartaric acid.The ammonium salt preferred version is selected from least a in ammonium nitrate, ammonium chloride or ammonium sulfate.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the preparation method of the toluene methylation catalyst of a kind of Increasing o-Xylene Output and paraxylene, comprise the following steps: a) under 20 ℃～95 ℃, the concentration that sodium type modenite is joined aequum is to process 0.5-24 hour in the organic acid soln of 0.05-5mol/L, washing after filtering, drying; B) concentration that above-mentioned modenite is joined aequum is in the ammonium salt solution of 0.05-5mol/L, and constant temperature was processed 0.5-24 hour under 40 ℃～100 ℃ conditions, washing after filtering, drying; C) above-mentioned modenite and binding agent are mixed in proportion aftershaping, obtained catalyst under 300-600 ℃ of condition in constant temperature calcining 1-12 hour.
In technique scheme, the ammonium salt preferred version is selected from least a in ammonium nitrate, ammonium chloride or ammonium sulfate.
Ortho para location base when the alkylated reaction due to the methyl on the toluene phenyl ring, the toluene methylation reaction only generates ortho-xylene and paraxylene in theory, and the ratio of ortho position product and contraposition product is 2: 1, and in actual product, a large amount of meta-xylene is from the isomerization reaction of ortho-xylene and paraxylene.Preparation method according to the toluene methylation catalyst of Increasing o-Xylene Output provided by the invention and paraxylene, control the sodium ions content of modenite by controlling the ammonium ion exchange condition, thereby after roasting became hydrogen type molecular sieve, the sour density and the acid site that have changed modenite distributed.Reduce like this probability of methyl alcohol generation side reaction in modenite 8 ring side openings (little toluene molecule can't enter because of the aperture), also reduced sour density, be conducive to suppress isomerization reaction, thereby improved the selective of ortho-xylene and paraxylene.
With catalyst of the present invention, be used for the alkylation of toluene methanol reaction, at 400 ℃ of reaction temperatures, reaction pressure 1.0MPa, air speed (WHSV) 6h -1Under hydrogen hydrocarbon mol ratio 1.0 conditions, its ortho-xylene selectively can reach 50%, higher than prior art more than 22% 1 times; Its Selectivity for paraxylene can reach 30%, higher than prior art with 24%, obtained technique effect preferably.
Illustrate embodiment of the present invention below by embodiment, but the present invention is not limited to this.
The specific embodiment
[embodiment 1-6]
Get respectively 30 gram silica alumina ratios and be and process filtration after certain hour, washing, drying in the certain density organic acid soln that 15 sodium type modenite (industrial goods) joins aequum, again it is joined in the certain density ammonium salt solution of aequum, the certain hour of constant temperature processing at a certain temperature carries out ion-exchange, filter rear washing, drying, obtain the modenite of different sodium exchange degrees; Modenite and binding agent that exchange is good mix in proportion aftershaping, obtain catalyst A-F after the constant temperature calcining certain hour, specifically see Table 1.
The preparation of table 1 catalyst
Embodiment 1 2 3 4 5 6
Organic acid Citric acid Oxalic acid Tartaric acid Citric acid Citric acid Citric acid
Organic acid concentration, mol/L 0.1 0.5 0.5 4 0.5 1
The acid treatment temperature, ℃ 90 90 90 30 80 50
The acid treatment time, hour 24 6 6 1 18 12
Ammonium salt Ammonium nitrate Ammonium nitrate Ammonium nitrate Ammonium chloride Ammonium chloride Ammonium sulfate
Ammonium salt concentration, mol/L 4 1 1 0.1 2 1
The ammonium exchange temperature, ℃ 50 90 90 95 90 80
Ammonium swap time, hour 4 6 6 24 1 4
Sodium ions content in NaHMor, % weight 0.10 0.36 0.34 2.3 0.60 0.92
Binding agent Aluminium oxide Aluminium oxide Aluminium oxide Ludox Aluminium oxide Boehmite
Catalyst forms, modenite/binding agent 15/85 50/50 30/70 90/10 70/30 80/20
Sintering temperature, ℃ 320 500 500 580 500 550
Roasting time, hour 2 4 4 10 6 6
The catalyst numbering A B C D E F
[embodiment 7-11]
Under 60 ℃, the concentration that the sodium type modenite (industrial goods) of getting respectively 30 gram Different Silicon aluminum ratios joins aequum is to process 6 hours in the citric acid solution of 0.5mol/L, washing after filtering, drying; It is joined in the certain density ammonium nitrate solution of aequum, the certain hour of constant temperature processing at a certain temperature carries out ion-exchange, filters rear washing, drying, obtains the modenite of different sodium exchange degrees again; Modenite and alumina binder that exchange is good mix in proportion aftershaping, and 500 ℃ of constant temperature calcinings obtain catalyst G-K after 6 hours, specifically see Table 2.
The preparation of table 2 catalyst
Embodiment 7 8 9 10 11
The modenite silica alumina ratio 10 10 25 30 72
Ammonium nitrate solution concentration, mol/L 1 0.5 1 0.5 0.2
The ammonium exchange temperature, ℃ 60 60 80 90 90
Ammonium swap time, hour 1 2 2 4 2
Sodium ions content in NaHMor, % weight 0.58 0.71 0.50 1.10 0.82
Catalyst forms, modenite/binding agent 40/60 60/40 70/30 90/10 80/20
The catalyst numbering G H I J K
[Comparative Examples]
Getting 30 gram silica alumina ratios and be the concentration that 10 sodium type modenite (industrial goods) joins aequum is in the ammonium nitrate solution of 1mol/L, processes at 95 ℃ of lower constant temperature and carries out ion-exchange in 4 hours, washing after filtering, drying; Repeat 3 ammonium exchanges under the same terms, in the h-mordenite that obtains (HM), sodium ions content is 0.02% weight again; HM and alumina binder are mixed aftershaping by 70/30, and 500 ℃ of constant temperature calcinings obtain comparative catalyst L after 6 hours.
[embodiment 12-23]
Investigated the performance of catalyst A-L catalysis alkylation of toluene methanol reaction on the fixed bed reaction evaluating apparatus, the mol ratio of raw material toluene and methyl alcohol is 2: 1, and loaded catalyst is 5g, 400 ℃ of reaction temperatures, reaction pressure 1.0MPa, charging air speed (WHSV) 6.0h -1, hydrogen hydrocarbon mol ratio 1.0.React 2 hours post analysis product compositions, the results are shown in table 3.
Figure BDA0000109783240000051
Figure BDA0000109783240000062
Figure BDA0000109783240000063
Table 3 different catalysts catalysis alkylation of toluene methanol reactivity worth
Catalyst Toluene conversion OX is selective PX is selective MX is selective
A 18.6 24 25 51
B 20.1 32 25 43
C 18.2 29 25 46
D 13.6 35 26 39
E 15.4 41 27 32
F 17.3 48 30 22
G 16.2 41 26 33
H 17.5 40 26 34
I 18.4 39 25 36
J 18.8 41 26 33
K 16.3 50 26 24
L 19.8 22 24 54

Claims (7)

1. the toluene methylation catalyst of an Increasing o-Xylene Output and paraxylene comprises following component in parts by weight:
A) h-mordenite that contains sodium ion 0.08-2.8% weight of 5～95 parts;
B) binding agent of 95～5 parts.
2. the toluene methylation catalyst of Increasing o-Xylene Output according to claim 1 and paraxylene is characterized in that in modenite, the mol ratio of silica and aluminium oxide is 8-80.
3. the toluene methylation catalyst of Increasing o-Xylene Output according to claim 1 and paraxylene is characterized in that binding agent is selected from least a in Ludox, boehmite, aluminium oxide.
4. the toluene methylation catalyst of Increasing o-Xylene Output according to claim 1 and paraxylene, is characterized in that h-mordenite sodium ions content scope is 0.10-2.0% weight.
5. the preparation method of the toluene methylation catalyst of Increasing o-Xylene Output according to claim 2 and paraxylene is characterized in that organic acid is selected from least a in citric acid, oxalic acid, tartaric acid.
6. the preparation method of the toluene methylation catalyst of Increasing o-Xylene Output claimed in claim 1 and paraxylene comprises the following steps:
A) under 20 ℃～95 ℃, the concentration that sodium type modenite is joined aequum is to process 0.5-24 hour in the organic acid soln of 0.05-5mol/L, washing after filtering, drying;
B) concentration that above-mentioned modenite is joined aequum is in the ammonium salt solution of 0.05-5mol/L, and constant temperature was processed 0.5-24 hour under 40 ℃～100 ℃ conditions, washing after filtering, drying;
C) above-mentioned modenite and binding agent are mixed aftershaping in required ratio, obtained catalyst under 300-600 ℃ of condition in constant temperature calcining 1-12 hour.
7. the preparation method of the toluene methylation catalyst of Increasing o-Xylene Output according to claim 6 and paraxylene is characterized in that ammonium salt is selected from least a in ammonium nitrate, ammonium chloride or ammonium sulfate.
CN201110369991.7A 2011-11-18 2011-11-18 Methylbenzene methylation catalyst for increasing production of o-xylene and p-xylene and preparation method thereof Active CN103120949B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104437599A (en) * 2013-09-24 2015-03-25 中国石油化工股份有限公司 Methylbenzene methylation catalyst and methylbenzene methylation method
CN107511163A (en) * 2016-06-18 2017-12-26 中国石油化工股份有限公司 Molecular sieve catalyst, preparation method and application

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CN1662485A (en) * 2002-06-27 2005-08-31 三菱丽阳株式会社 Production method of dimethylamine
CN101340976A (en) * 2005-12-22 2009-01-07 法国石油公司 Dual zeolite catalyst comprising a group VIII metal and a group IIIV metal and its use in isomerization of aromatic C8 compounds
CN101898145A (en) * 2009-05-27 2010-12-01 中国石油化工股份有限公司 Alkyl aromatic hydrocarbon isomerization catalyst and preparation method thereof

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US6525234B1 (en) * 2000-11-21 2003-02-25 Exxonmobil Oil Corporation Process for liquid phase aromatics alkylation comprising in-situ catalyst reactivation with polar compounds
CN1662485A (en) * 2002-06-27 2005-08-31 三菱丽阳株式会社 Production method of dimethylamine
CN101340976A (en) * 2005-12-22 2009-01-07 法国石油公司 Dual zeolite catalyst comprising a group VIII metal and a group IIIV metal and its use in isomerization of aromatic C8 compounds
CN101898145A (en) * 2009-05-27 2010-12-01 中国石油化工股份有限公司 Alkyl aromatic hydrocarbon isomerization catalyst and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104437599A (en) * 2013-09-24 2015-03-25 中国石油化工股份有限公司 Methylbenzene methylation catalyst and methylbenzene methylation method
CN107511163A (en) * 2016-06-18 2017-12-26 中国石油化工股份有限公司 Molecular sieve catalyst, preparation method and application

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