CN1421271A - Molecular sieve catalyst for synthesizing methanol into durene and its prepn and application - Google Patents
Molecular sieve catalyst for synthesizing methanol into durene and its prepn and application Download PDFInfo
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- CN1421271A CN1421271A CN02155481A CN02155481A CN1421271A CN 1421271 A CN1421271 A CN 1421271A CN 02155481 A CN02155481 A CN 02155481A CN 02155481 A CN02155481 A CN 02155481A CN 1421271 A CN1421271 A CN 1421271A
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- molecular sieve
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- acid
- durol
- methyl alcohol
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The molecular sieve catalyst for synthesizing methanol into durene is ZSM-5 type with molar Si/Al ratio of 13-50, strong/weak acid ratio of 1.03-1.30, adsorption amount to cyclohexane of 5.95-6.25 wt%, said adsorption amount to n-hexane of 8.95-9.15 wt%. The hydrogen-type molecular sieve, assistant and nitric acid are mixed and kneaded, and the mixture is formed, stoved, crushed, roasted, soaking in acid solution, stoved and roasted to obtain the catalyst. The present invention has the advantages of simple preparation process, high selectivity of the catalyst, and the durene content in the product as high as 20%.
Description
Affiliated field:
The invention belongs to a kind of preparation and application of synthetic durol molecular sieve catalyst, relate to a kind of preparation and application specifically by the synthetic durol molecular sieve catalyst of methyl alcohol.
Background technology:
Methyl alcohol is a kind of abundant raw material of industry of originating, and is C
1The important component part of chemistry is a very active subject to the synthetic of it with transforming always.Along with the fast development of China's Petrochemical, for improving the competitiveness, also towards maximization, energy-saving development, output continues to increase China's methanol production in recent years.At present supply exceed demand in methyl alcohol market, and new device also is constructed and put into operation continuing, therefore, the exploitation of Downstream Products of Methanol has crucial meaning (list of references 1: Ma Bing for the development of methanol industry, modern chemical industry, the present situation of China's methanol industry and future, N07.P1.2000).Methyl alcohol is converted into hydro carbons under the effect of catalyst be to study field comparatively widely.At first proposing to adopt the five-membered ring mesopore ZSM-5 molecular sieve catalyst of being made up of silicon-oxy tetrahedron that methyl alcohol is carried out height by mobil company in early days selects to transform the high-quality gasoline of generation, makes oil fossil fuel such as natural gas and coal etc. in addition can become the effective energy.In the catalytic conversion process of methyl alcohol, along with the difference of catalyst performance, product is formed very big variation.In our research, adopted the acid dip method that the ZSM-5 molecular sieve is carried out upgrading, prepared catalyst presents good selectivity to durol in the conversion reaction of methyl alcohol.At reaction condition is P=2.0Mpa, T380 ℃, LHSV=2.0, and methanol conversion remains on 99%, and the content of durol can reach 20% in the product.Durol is a sharp white monoclinic crystal, is oxidized to PMA or pyromellitic acid dianhydride.Make polyimide resin, dyestuff, plasticizer, surfactant, delustering agent, curing agent etc.It is important Organic Chemicals, usually durol is to be raw material with reformation carbon ten, makes by rectifying, enrichment, crystallization, separation, because equal four benzene content are very low in the C10 aromartic, therefore the whole process of production investment is big, energy consumption is high, so method has limited the production of durol.So the method that methyl alcohol is catalytically conveted to durol and gasoline will be to the replenishing of durol production method, and also be simultaneously the effective ways that improve the methyl alcohol added value.Methanol conversion at first is the exothermic reaction that belongs to hydrocarbon under the acid catalysis, and its reactivity worth is subjected to the influence of acid catalysis, and strong acidic site has determined the arene content in the product (list of references 5 Zhu Jianhuas, petroleum journal (PETROLEUM PROCESSING), 14 (1), 46 (1998)).Therefore the selectivity that can in reaction, improve durol of acid amount and the acid distribution by the modulation zeolite molecular sieve under certain condition.What we adopted is the acid dip roasting method, is about to inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid by incipient impregnation, and high-temperature roasting can reach the purpose that improves the strong acid amount then.The selectivity of catalyst durol in the conversion reaction of methyl alcohol of making of method can reach 20% thus, and all the other products are high-knock rating gasoline.
Summary of the invention
The purpose of this invention is to provide a kind of molecular sieve catalyst that is converted into durol and gasoline by the methyl alcohol high selectivity and its production and application.Molecular sieve catalyst of the present invention is the ZSM-5 type, and the mole silica alumina ratio is 13-50, and ratio strong, weak acid is 1.03-1.30.Catalyst is 5.95-6.25 (wt) % to the adsorbance of cyclohexane, is 8.95-9.15 (wt) % to the adsorbance of n-hexane.
Preparation of catalysts method of the present invention comprises the steps:
(1) at first with nSiO
2/ nAl
2O
3Than for the Hydrogen ZSM-5 molecular sieve of 24-78 at 520-540 ℃ of following roasting 3-5 hour to remove the impurity of its physical absorption;
(2) molecular sieve after the processing of (1) step is mixed for the ratio of 72-63: 28-37 in molar ratio with auxiliary agent, evenly grind;
(3) drips of solution that nitric acid is mixed with 2-4% adds to mix in the ground material of (2) step and pinches suitable back extrusion modling, 100-120 ℃ of oven dry down;
(4) material after the oven dry of (3) step is crushed to the 10-40 order, then at 500-520 ℃ of roasting 3-5 hour, to take off nitric acid and moisture;
(5) inorganic acids is mixed with the solution of 0.5-2.0mol/L;
(6) under 60-80 ℃ electromagnetic agitation, carry out 1-3 hour dipping than the ratio of 3-5ml acid solution in catalyst weight 1 gram;
(7) behind the basic evaporate to dryness of maceration extract, it was kept in 100-120 ℃ baking oven 3-8 hour, made catalyst then at 350-400 ℃ of roasting 3-5 hour.Aforesaid inorganic acid is sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid etc.Aforesaid auxiliary agent is boehmite, γ-Al
2O
3Deng molecular sieve molded auxiliary agent commonly used.Process conditions when catalyst of the present invention is used for the synthetic durol of methyl alcohol are:
Pressure P=1.0-2.0Mpa; Temperature T=360 ℃-380 ℃; Air speed LHSV=1.0-2.0h
-1, advantage of the present invention is:
(1) adopt the catalyst of upgrading molecular sieve ZSM-5 first, and the preparation method is simple as methyl alcohol system durol and gasoline.
(2) catalyst selectivity height, durol content can be up to 20% in the product;
(3) product is after isolating durol, and residue is a high-knock rating gasoline.
The specific embodiment:
Embodiment 1
(1) earlier be 20 Hydrogen ZSM-5 molecular sieve 540 ℃ of following roastings 3 hours to remove the impurity of its absorption with 20 gram Si/Al (mol);
(2) 13 gram molecules sieve is restrained γ-Al with 7
2O
3Put into mortar simultaneously and mix, evenly grind;
(3) 3% salpeter solution is dripped in the good material of mill, mix and pinch suitably, be squeezed into the bar column type of Φ 2, insert in the baking oven and dry down in 120 ℃ with manual spiral banded extruder;
(4) again the strip molecular sieve is crushed to the 10-40 order and puts into Muffle furnace and be warming up to 530 ℃ of roastings 5 hours,, treat that temperature is reduced to below 60 ℃ can take out to take off nitric acid and moisture;
(5) accurately take by weighing 32% hydrochloric acid, 3.42 grams and put into volumetric flask, add deionized water is mixed with 1mol/L to 30ml solution; Take by weighing 10 molecular sieves that make of gram (4) step and put into conical flask, under 80 ℃, keeping 2 hours on the electromagnetic agitation heater, substantially evaporate to dryness;
(6) again it is inserted keep 5 hours in 110 ℃ the baking oven after, put into Muffle furnace and made catalyst in 3 hours in 350 ℃ of roastings, be numbered JS-01.The mole silica alumina ratio is 13.28, and it is strong, the ratio of weak acid is 1.03;
(7) this catalyst is pulverized be the 20-40 order, measure 5ml and pack in the reactor, reaction condition is as follows: P=2.0MPa temperature T=360 ℃; Air speed LHSV=1.0h
-1, sample analysis after 30 hours is carried out in reaction, the results are shown in Table 3.
Embodiment 2
(1) at first be 52.5 Hydrogen ZSM-5 molecular sieve 540 ℃ of following roastings 3 hours to remove the impurity of its absorption with 20 gram Si/Al (mol);
(2) 14 gram molecules sieve is restrained γ-Al with 6
2O
3Put into mortar simultaneously and mix, evenly grind;
(3) 3% salpeter solution is dripped in the good material of mill, mix and pinch suitably, be squeezed into the bar column type of Φ 2, insert in the baking oven and dry down in 105 ℃ with manual spiral banded extruder;
(4) again the strip molecular sieve is crushed to the 10-40 order and puts into Muffle furnace and be warming up to 510 ℃ of roastings 3 hours,, treat that temperature is reduced to below 60 ℃ can take out to take off nitric acid and moisture;
(5) accurately take by weighing 36% nitric acid, 10.5 grams and put into volumetric flask, add deionized water, shake up to the solution that 30ml is mixed with 2mol/L; Take by weighing 10 molecular sieves that make of gram (4) step and put into conical flask, under 60 ℃, keeping 2 hours evaporate to dryness on the electromagnetic agitation heater;
(6) again it is inserted keep 7 hours in 105 ℃ the baking oven after, put into Muffle furnace and got final product in 3 hours in 400 ℃ of roastings, being numbered J-Q-02 mole silica alumina ratio is 36.73, it is strong, the ratio of weak acid is 1.23;
(7) this catalyst is pulverized be the 20-40 order, measure 5ml and pack in the reactor, reaction condition is as follows: P=2.0MPa temperature T=370 ℃; Air speed LHSV=1.2h
-1, sample analysis after 30 hours is carried out in reaction, the results are shown in Table 3.Embodiment 3
(1) at first be 35.3 Hydrogen ZSM-5 molecular sieve 540 ℃ of following roastings 3 hours to remove the impurity of its absorption with 20 gram Si/Al (mol);
(2) 14.4 gram molecules sieve is put into mortar simultaneously with the thin water aluminium oxide of 5.6 gram plans and mix, evenly grind;
(3) 2% salpeter solution is dripped in the good material of mill, mix and pinch suitably, be squeezed into the bar column type of Φ 2, insert in the baking oven and dry down in 115 ℃ with manual spiral banded extruder;
(4) again the strip molecular sieve is crushed to the 10-40 order and puts into Muffle furnace and be warming up to 520 ℃ of roastings 3 hours,, treat that temperature is reduced to below 60 ℃ can take out to take off nitric acid and moisture;
(5) accurately take by weighing 98% sulfuric acid, 3.0 grams and put into volumetric flask, add deionized water is mixed with 1mol/L to 30ml solution; Take by weighing 10 molecular sieves that make of gram (4) step and put into conical flask, under 60 ℃, keeping 2 hours evaporate to dryness on the electromagnetic agitation heater;
(6) again it is inserted keep 8 hours in 120 ℃ the baking oven after, put into Muffle furnace and made catalyst in 5 hours in 310 ℃ of roastings, be numbered JS-3, a mole silica alumina ratio is 25.42, it is strong, the ratio of weak acid is 1.29;
(7) this catalyst is pulverized be the 20-40 order, measure 5ml and pack in the reactor, reaction condition is as follows: P=1.5MPa temperature T=380 ℃; Air speed LHSV=1.5h
-1, sample analysis after 30 hours is carried out in reaction, the results are shown in Table 3.
Embodiment 4
(1) at first be 67.8 Hydrogen ZSM-5 molecular sieve 540 ℃ of following roastings 3 hours to remove the impurity of its absorption with 20 gram Si/Al (mol);
(2) 12.8 gram molecules sieve is restrained γ-Al with 7.2
2O
3Put into mortar simultaneously and mix grinding;
(3) 3% salpeter solution is dripped in the good material of mill, mix and pinch suitably, be squeezed into the bar column type of Φ 2, insert in the baking oven and dry down in 120 ℃ with manual spiral banded extruder;
(4) again the strip molecular sieve is crushed to the 10-40 order and puts into Muffle furnace and be warming up to 520 ℃ of roastings 3 hours,, treat that temperature is reduced to below 60 ℃ can take out to take off nitric acid and moisture;
(5) accurately take by weighing 85% phosphoric acid, 3.45 grams and put into volumetric flask, add deionized water is mixed with 1mol/L to 30ml solution; Take by weighing 10 molecular sieves that make of gram (4) step and put into conical flask, under 80 ℃, keeping 2 hours evaporate to dryness on the electromagnetic agitation heater;
(6) again it is inserted keep 6 hours in 120 ℃ the baking oven after, put into Muffle furnace and made catalyst in 3 hours in 350 ℃ of roastings, be numbered JS-4, a mole silica alumina ratio is 43.42, it is strong, the ratio of weak acid is 1.22;
(7) this catalyst is pulverized be the 20-40 order, measure 5ml and pack in the reactor, reaction condition is as follows: P=1.5MPa temperature T=360 ℃; Air speed LHSV=1.6h
-1, sample analysis after 30 hours is carried out in reaction, the results are shown in Table 3.
Embodiment 5
(1) earlier be 32.3 Hydrogen ZSM-5 molecular sieve 540 ℃ of following roastings 3 hours to remove the impurity of its absorption with 20 gram Si/Al (mol);
(2) 12.8 gram molecules sieve is restrained γ-Al with 7.2
2O
3Put into mortar simultaneously and mix, evenly grind;
(3) 3% salpeter solution is dripped in the good material of mill, mix and pinch suitably, be squeezed into the bar column type of Φ 2, insert in the baking oven and dry down in 120 ℃ with manual spiral banded extruder;
(4) the strip molecular sieve is crushed to the 10-40 order and puts into Muffle furnace and be warming up to 520 ℃ of roastings 3 hours, to take off nitric acid and moisture, treats that temperature is reduced to below 60 ℃ can take out;
(5) take by weighing 85% phosphatase 11 .73 gram and put into volumetric flask, add deionized water and be mixed with the solution of 0.5mol/L to 30ml, take by weighing the molecular sieve that 10 gram (4) steps made and put into conical flask, under 60 ℃, keeping 2 hours evaporate to dryness on the electromagnetic agitation heater;
(6) it is inserted keep 5 hours in 110 ℃ the baking oven after, put into Muffle furnace and made catalyst in 3 hours in 400 roasting roastings, be numbered JS-5, a mole silica alumina ratio is 20.12, it is strong, the ratio of weak acid is 1.21;
(7) catalyst is pulverized be the 20-40 order, measure 5ml and pack in the reactor, reaction condition is as follows: P=1.0MPa temperature T-370 ℃; Air speed LHSV=1.3h
-1, sample analysis after 30 hours is carried out in reaction, the results are shown in Table 3.The acid characterization of embodiment 1-5 catalyst:
Utilization NH
3-TPD characterizes strong, faintly acid, and detailed process is as follows: the 0.2g 20-40 purpose of packing in the stainless steel reactor of φ 8 * 300mm catalyst is feeding high-purity N
2After be warming up to 500 ℃ and keep 1h, lowering the temperature then begins to switch absorption NH in 50 ℃
3Until saturated, switch to high-purity N again
2Purge 40min down at 50 ℃ and remove physical absorption, the speed with 25 ℃/min is warming up to 600 ℃ of (high-purity N at last
2Flow velocity is 35ml/min) finish desorption.The suction of molecular sieve, desorption rate adopt TCD to detect, and data are handled in conjunction with the HCl solution absorption titration of external standard method and 0.1M and calculated and get.With the desorption rate below 300 ℃ is the weak acid amount, and desorption rate is the strong acid amount more than 300 ℃.Table 1 is the acid characterization result of catalyst.The adsorbance of embodiment 1-5 catalyst characterizes:
In order to characterize the architectural characteristic of catalyst, catalyst has been carried out the mensuration of adsorbance.At first with the N of institute's test sample product at 300 ℃
2Dry purge under the atmospheric condition is evacuated to vacuum meter with adsorbent equipment then and is designated as 0.07Mpa, begins to adsorb selected adsorbate and keeps 3 hours, weighs then, calculates adsorbance.Table 2 is the adsorbance determination data of embodiment catalyst to cyclohexane, n-hexane.Table 1
Table 2
Table 3
Claims (5)
1. a molecular sieve catalyst that is used for the synthetic durol of methyl alcohol is characterized in that molecular sieve catalyst of the present invention is the ZSM-5 type, and the mole silica alumina ratio is 13-50, and ratio strong, weak acid is 1.03-1.30.Catalyst is 5.95-6.25 (wt) % to the adsorbance of cyclohexane, is 8.95-9.15 (wt) % to the adsorbance of n-hexane.
2. a preparation that is used for the molecular sieve catalyst of the synthetic durol of methyl alcohol is characterized in that comprising the steps;
(1) earlier with nSiO
2/ nAl
2O
3Than for the Hydrogen ZSM-5 molecular sieve of 24-78 at 520-540 ℃ of following roasting 3-5 hour to remove the impurity of its physical absorption;
(2) molecular sieve after the processing of (1) step mixes for the ratio of 72-63: 28-37 in molar ratio with auxiliary agent, evenly grinds;
(3) the nitric acid drips of solution that is mixed with 2-4% adds to mix in the ground material of (2) step and pinches suitable back extrusion modling, 100-120 ℃ of oven dry down;
Material after the oven dry of (4) (3) steps is crushed to the 10-40 order, then at 500-520 ℃ of roasting 3-5 hour, to take off nitric acid and moisture;
(5) inorganic acids is mixed with the solution of 0.5-2.0mol/L;
(6) under 60-80 ℃ electromagnetic agitation, carry out 1-3 hour dipping than the ratio of 3-5ml acid solution in catalyst weight 1 gram;
(7) behind the basic evaporate to dryness of maceration extract, it was kept in 100-120 ℃ baking oven 3-8 hour, made catalyst then at 350-400 ℃ of roasting 3-5 hour.
3. a kind of preparation that is used for the molecular sieve catalyst of the synthetic durol of methyl alcohol as claimed in claim 2 is characterized in that described inorganic acid is sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid.
4. a kind of preparation that is used for the molecular sieve catalyst of the synthetic durol of methyl alcohol as claimed in claim 2 is characterized in that described auxiliary agent is boehmite, γ-Al
2O
3
5. a kind of application that is used for the molecular sieve catalyst of the synthetic durol of methyl alcohol as claimed in claim 1 is characterized in that process conditions are:
Pressure P=1.0-2.0Mpa, temperature T=360 ℃-380 ℃, air speed LHSV=1.0-2.0h
-1
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021554811A CN1162220C (en) | 2002-12-16 | 2002-12-16 | Molecular sieve catalyst for synthesizing methanol into durene and its prepn and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021554811A CN1162220C (en) | 2002-12-16 | 2002-12-16 | Molecular sieve catalyst for synthesizing methanol into durene and its prepn and application |
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|---|---|
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| CN1162220C CN1162220C (en) | 2004-08-18 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301794C (en) * | 2004-08-06 | 2007-02-28 | 董家禄 | Molecular sieve type catalyst of low carbon olefine by catalizing thermo cracking process |
| CN103864562A (en) * | 2014-02-24 | 2014-06-18 | 中国海洋石油总公司 | Method for preparing durene by using methyl alcohol |
| CN105457669A (en) * | 2015-12-10 | 2016-04-06 | 中国海洋石油总公司 | Methanol to durene catalyst and preparation method thereof |
| CN111116296A (en) * | 2019-12-12 | 2020-05-08 | 浙江大学 | Method for separating benzene and cyclohexane |
-
2002
- 2002-12-16 CN CNB021554811A patent/CN1162220C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301794C (en) * | 2004-08-06 | 2007-02-28 | 董家禄 | Molecular sieve type catalyst of low carbon olefine by catalizing thermo cracking process |
| CN103864562A (en) * | 2014-02-24 | 2014-06-18 | 中国海洋石油总公司 | Method for preparing durene by using methyl alcohol |
| CN103864562B (en) * | 2014-02-24 | 2015-07-08 | 中国海洋石油总公司 | Method for preparing durene by using methyl alcohol |
| CN105457669A (en) * | 2015-12-10 | 2016-04-06 | 中国海洋石油总公司 | Methanol to durene catalyst and preparation method thereof |
| CN105457669B (en) * | 2015-12-10 | 2018-06-26 | 中国海洋石油总公司 | A kind of methanol durol catalyst and preparation method thereof |
| CN111116296A (en) * | 2019-12-12 | 2020-05-08 | 浙江大学 | Method for separating benzene and cyclohexane |
| CN111116296B (en) * | 2019-12-12 | 2021-02-19 | 浙江大学 | Method for separating benzene and cyclohexane |
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| Publication number | Publication date |
|---|---|
| CN1162220C (en) | 2004-08-18 |
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