CN102304011B - Method for producing 1,2,4-trimethylbenzene by C9 aromatic hydrocarbon isomerization - Google Patents
Method for producing 1,2,4-trimethylbenzene by C9 aromatic hydrocarbon isomerization Download PDFInfo
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Abstract
The invention discloses a method for producing 1,2,4-trimethylbenzene by C9 aromatic hydrocarbon isomerization, belonging to the technical field of chemical industry. The method comprises the following steps of: dehydrogenizing the C9 aromatic hydrocarbon; then conveying hemimelitene, mesitylene and o-methyl ethylbenzene which are obtained by rectifying into an isomerization reactor; carrying outa catalysis reaction at a temperature in a range of 260-410 DEG C under 0.2-3.5 Mpa; isomerising parts of the hemimelitene and the mesitylene to form 1,2,4-trimethylbenzene; and rectifying and separating to obtain the 1,2,4-trimethylbenzene. The conversion per pass of the method provided by the invention can reach 45% and the method can produce much more 1,2,4-trimethylbenzene by utilizing the C9aromatic hydrocarbon.
Description
Technical field
The present invention relates to a kind of production method of Chemicals, particularly the production method of unsym-trimethyl benzene belongs to chemical technology field.
Background technology
C9 aromatic hydrocarbons has another name called heavy aromatics, and for a kind of multiple aromatic composition that contains 9 carbon atoms is arranged, its molecular formula is C9H12, and C9 aromatic hydrocarbons is the by product that produces in the Crude Oil Processing, main reformer and cracker from the refinery.C9 aromatic hydrocarbons contains a large amount of unsym-trimethyl benzenes, sym-trimethylbenzene, hemimellitene, o-methylethylbenzene, m-methyl ethylbenzene, p-methyl-ethylbenzene, n-proplbenzene and isopropyl benzene etc., wherein the total content of unsym-trimethyl benzene, sym-trimethylbenzene and hemimellitene is about 80%, be the precious resources of development fine chemistry industry, have very high added value.And unsym-trimethyl benzene (1,2,4 one trimethylbenzenes) in C9 aromatic hydrocarbons, account for 35%～40%, because the boiling point of unsym-trimethyl benzene is 169.4 ℃, the boiling point of the o-methylethylbenzene nearest with boiling point (165.0 ℃ of boiling points) and hemimellitene (176.1 ℃ of boiling points) differs greatly, therefore can directly obtain the very high unsym-trimethyl benzene of purity by the method for rectifying, product purity can reach more than 98.5% (mass percent).And unsym-trimethyl benzene is the raw material of producing trimellitic acid 1,2-anhydride, therefore, take full advantage of abundant unsym-trimethyl benzene resource and produce trimellitic acid 1,2-anhydride, not only can take full advantage of the heavy aromatics resource of China's abundant, but also can alleviate China's trimellitic acid 1,2-anhydride situation in short supply greatly.Simultaneously, unsym-trimethyl benzene is again the important fine chemical material of a kind of high quality, high added value, and (mainly) can be used for synthetic resins processed, dyestuff, medicine, softening agent, high-grade automobile finish, special varnish etc., on the whole, China is bigger to the demand of this series products.It is reported that present domestic unsym-trimethyl benzene yearly capacity is lower, major part will rely on import to remedy, so this product has good market development prospect at home, is the project that the national industrial policies emphasis is encouraged.
The production of existing unsym-trimethyl benzene, each big manufacturer mainly makes by rectification method, by the difference realization separation of boiling point.Its weak point is: owing to also contain other a large amount of components in the C9 aromatic hydrocarbons, although on industrial chain, by product after the rectifying is still recycling, but as the producer that produces unsym-trimethyl benzene, complete and the production unit corresponding derived product of byproduct may not be arranged, therefore, in the resultant product after the rectifying, some can only be sold to other producers at a low price.Cause the production cost of manufacturer higher.How more reasonably to utilize C9 aromatic hydrocarbons, the output unsym-trimethyl benzene is unsym-trimethyl benzene manufacturer problem demanding prompt solution more.
Summary of the invention
The purpose of this invention is to provide a kind of C9 aromatics isomerization and produce the method for unsym-trimethyl benzene, can take full advantage of C9 aromatic hydrocarbons, improve the productive rate of unsym-trimethyl benzene.
The object of the present invention is achieved like this: the C9 aromatics isomerization is produced the method for unsym-trimethyl benzene, comprises the steps:
1) purity is taken off light processing more than or equal to 90% C9 aromatic hydrocarbons in lightness-removing column, the working temperature of control lightness-removing column is 166 ℃～168 ℃, after making boiling point be lower than 166 ℃ o-methylethylbenzene, m-methyl ethylbenzene, p-methyl-ethylbenzene, sym-trimethylbenzene, n-proplbenzene and isopropyl benzene vaporization and leaving lightness-removing column from cat head, enter first rectifying tower; The boiling point that keeps at the bottom of the tower of lightness-removing column is higher than 168 ℃ unsym-trimethyl benzene and hemimellitene and is delivered to second rectifying tower;
2) in second rectifying tower, rectification temperature is 169.5 ℃～175 ℃, and unsym-trimethyl benzene leaves and is collected from the second rectifying tower top, and second rectifier bottoms keeps hemimellitene;
3) in first rectifying tower, rectification temperature is 162 ℃～164 ℃, keeps sym-trimethylbenzene and o-methylethylbenzene at the bottom of the tower;
4) with above-mentioned steps 2) and the bottom product of step 3) send into simultaneously in the airtight isomerization reactor, carry out catalyzed reaction, catalyzer is arranged in the isomerization reactor with the form of fixed bed, reactant flow is passed through fixed bed with liquid form; The isomerization reactor internal pressure is 0.2MPa～3.5MPa, temperature of reaction is 260 ℃～410 ℃, step 2) and the bottom product Continuous Flow of step 3) cross fixed bed, isomerization reaction takes place under catalyst action, make part hemimellitene, the isomerization of sym-trimethylbenzene recurring structure and become unsym-trimethyl benzene, simultaneously, there is part o-methylethylbenzene isomery to become p-methyl-ethylbenzene and m-methyl ethylbenzene;
5) with above-mentioned steps 4) reaction product again rectifying obtain unsym-trimethyl benzene.Above-mentioned steps 5) can be achieved by following two kinds of methods, one: by isomerization reaction product constantly is input to lightness-removing column, after taking off gently, send in second rectifying tower, rectifying obtains unsym-trimethyl benzene in second rectifying tower, and bottom product is sent into again and carried out circulating reaction in the isomerization reactor.They are two years old, by isomerization reaction product being input to the 3rd rectifying tower, in the 3rd rectifying tower, 166 ℃～168 ℃ of rectification temperatures, the isomerization product of sym-trimethylbenzene, o-methylethylbenzene and o-methylethylbenzene is left from the top of the 3rd rectifying tower, and circulation enter in the isomerization reactor; The unsym-trimethyl benzene and the hemimellitene that keep at the bottom of the tower of the 3rd rectifying tower are sent in the 4th rectifying tower, the rectification temperature of the 4th rectifying tower is 169.5 ℃～175 ℃, unsym-trimethyl benzene leaves and is collected from the 4th rectifying tower top, and the hemimellitene that the 4th rectifier bottoms keeps circulates again and enters in the isomerization reactor.
C9 aromatic hydrocarbons can be the petroleum cracking product, also can be oil at the bottom of the tower after described petroleum cracking product extracts sym-trimethylbenzene; Each component all is mononuclear aromatics structures that alkyl links to each other with phenyl ring in the C9 aromatic hydrocarbons, because the plane at carbon atom place two the πDian Zi clouds that distributing up and down in the phenyl ring, alkyl has the electronics of pushing away to phenyl ring, induce and hyperconjugation by it, electronic cloud is pushed to phenyl ring, the cloud density of whole phenyl ring is increased.Different C9 aromatic hydrocarbons is owing to alkyl pattern and position is different, and it is also different with spatial obstacle to have determined that the phenyl ring cloud density distributes.Sym-trimethylbenzene in the trimethylbenzene, three methyl on its phenyl ring are evenly distributed, and the electronic cloud of the conjugated system that itself and phenyl ring form is uniformly, so the spatial obstacle maximum; Three methyl on the unsym-trimethyl benzene phenyl ring distribute and take second place, and the electronic cloud of the conjugated system that forms with phenyl ring is not really even, and its spatial obstacle is bigger; Three methyl on the hemimellitene phenyl ring distribute least even, and the electronic cloud of the conjugated system that forms with phenyl ring is also least even, so the spatial obstacle minimum.The present invention is by isomerization reaction, the easier generation unsym-trimethyl benzene of hemimellitene, sym-trimethylbenzene is difficulty relatively, but because the unsym-trimethyl benzene in the system is constantly separated from resultant, remaining sym-trimethylbenzene and hemimellitene can turn back to again carries out recycle in the system, make isomerization reaction to carry out to the direction of continuous generation unsym-trimethyl benzene, because the boiling point of o-methylethylbenzene is 165 ℃, differ too little for 164.7 ℃ with the boiling point of sym-trimethylbenzene, be difficult to realize effectively separating by common rectifying, and in isomerization reaction, o-methylethylbenzene partly generates m-methyl ethylbenzene and p-methyl-ethylbenzene, the boiling point of m-methyl ethylbenzene and p-methyl-ethylbenzene and the boiling point of unsym-trimethyl benzene differ greatly, can carry out rectifying separation more easily, o-methylethylbenzene also can carry out rectifying separation easily with unsym-trimethyl benzene, therefore no matter o-methylethylbenzene isomery whether, and its generation to unsym-trimethyl benzene can not impact with separating all; Because o-methylethylbenzene content in raw material itself is just fewer, have only about 5%, therefore, o-methylethylbenzene accumulation phenomenon can not occur, it is comparatively economic way that the reservation o-methylethylbenzene enters isomerization reactor.The per pass conversion of this method can be up to 45%.It can take full advantage of C9 aromatic hydrocarbons, can make unsym-trimethyl benzene more.
It is 8～12 zeolite that above-mentioned catalysagen material package is drawn together water, water glass, Tai-Ace S 150, silica alumina ratio, and raw material mixes the back and forms colloid, and becoming the glue temperature is 40～75 ℃, time is 2～10 hours, crystallization temperature is 150～220 ℃, and crystallization time is 8～20 hours, obtains synthetic zeolite; Again through ion-exchange removal part A l atom wherein, the mol ratio that makes silicon and aluminium is 10～150 with synthetic zeolite, and sodium is taken off in washing again, and it is 20～90% that the sodium degree is taken off in control, and high-temperature roasting obtains pulverous catalyzer then.The purpose of removing part A l atom is to increase the acidic catalyst function, improve catalyst activity, in catalyzed reaction, synthetic zeolite provides acid function for isomerization, the position of methyl is shifted, part sym-trimethylbenzene and hemimellitene are isomerizated into unsym-trimethyl benzene, and then can utilize rectification method that unsym-trimethyl benzene is separated.
The carrier of catalyzer described above is aluminum oxide, and described aluminum oxide and catalyzer, water, mineral binder bond are mixed into paste, extrusion moulding on banded extruder again, after the moulding in 110～150 ℃ of down oven dry, activated again after, place in the fixed bed.In this step, the carrier consumption is 10～50% of all solids thing weight; Mineral binder bond is at least a in water glass, aluminum phosphate, calcium oxide, magnesium oxide and the calcium sulfate.
Description of drawings
Fig. 1 is a kind of fundamental diagram of the present invention.
Fig. 2 is the another kind of fundamental diagram of the present invention.
Wherein, 1 lightness-removing column, 2 first rectifying tower, 3 second rectifying tower, 4 isomerization reactors, 5 the 3rd rectifying tower, 6 the 4th rectifying tower.
Embodiment
Embodiment 1
The C9 aromatics isomerization is produced the method for unsym-trimethyl benzene, and step is as follows:
1) purity that petroleum cracking is produced is taken off light processing more than or equal to 90% C9 aromatic hydrocarbons in lightness-removing column 1, the working temperature of control lightness-removing column 1 is 166 ℃～168 ℃ and (is difficult to accomplish to control at certain concrete exact value because temperature is controlled, therefore, it is as long as fluctuation all is suitable in certain interval range, down together), after making boiling point be lower than 166 ℃ o-methylethylbenzene, m-methyl ethylbenzene, p-methyl-ethylbenzene, sym-trimethylbenzene, n-proplbenzene and isopropyl benzene vaporization and leaving lightness-removing column 1 from cat head, enter first rectifying tower 2; The boiling point that keeps at the bottom of the tower of lightness-removing column 1 is higher than 168 ℃ unsym-trimethyl benzene and hemimellitene and is delivered to second rectifying tower 3;
2) in second rectifying tower 3, rectification temperature is 169.5 ℃～175 ℃, and unsym-trimethyl benzene leaves and is collected from second rectifying tower, 3 tops, and second rectifying tower, 3 bottoms keep hemimellitene;
3) in first rectifying tower 2, rectification temperature is 162 ℃～164 ℃, keeps sym-trimethylbenzene and o-methylethylbenzene at the bottom of the tower;
4) with above-mentioned steps 2) and the bottom product of step 3) send into simultaneously in the airtight isomerization reactor 4, carry out catalyzed reaction, catalyzer is arranged in the isomerization reactor 4 with the form of fixed bed, reactant flow is passed through fixed bed with liquid form; The isomerization reactor internal pressure is 0.2MPa, temperature of reaction is 260～270 ℃, step 2) and the bottom product Continuous Flow of step 3) cross fixed bed, isomerization reaction takes place under catalyst action, make part hemimellitene, the isomerization of sym-trimethylbenzene recurring structure and become unsym-trimethyl benzene, simultaneously, there is part o-methylethylbenzene isomery to become p-methyl-ethylbenzene and m-methyl ethylbenzene;
5) reaction product that step 4) is obtained constantly is input to lightness-removing column 1, sends in second rectifying tower 3 after taking off gently, and rectifying obtains unsym-trimethyl benzene in second rectifying tower 3, and bottom product is sent into again and carried out circulating reaction in the isomerization reactor 4.
The C9 aromatics isomerization is produced the method for unsym-trimethyl benzene, and step is as follows:
1) purity that petroleum cracking is produced is taken off light processing more than or equal to 90% C9 aromatic hydrocarbons in lightness-removing column 1, the working temperature of control lightness-removing column 1 is 166 ℃～168 ℃, after making boiling point be lower than 166 ℃ o-methylethylbenzene, m-methyl ethylbenzene, p-methyl-ethylbenzene, sym-trimethylbenzene, n-proplbenzene and isopropyl benzene vaporization and leaving lightness-removing column 1 from cat head, enter first rectifying tower 2; The boiling point that keeps at the bottom of the tower of lightness-removing column 1 is higher than 168 ℃ unsym-trimethyl benzene and hemimellitene and is delivered to second rectifying tower 3;
2) in second rectifying tower 3, rectification temperature is 169.5 ℃～175 ℃, and unsym-trimethyl benzene leaves and is collected from second rectifying tower, 3 tops, and second rectifying tower, 3 bottoms keep hemimellitene;
3) in first rectifying tower 2, rectification temperature is 162 ℃～164 ℃, keeps sym-trimethylbenzene and o-methylethylbenzene at the bottom of the tower;
4) with above-mentioned steps 2) and the bottom product of step 3) send into simultaneously in the airtight isomerization reactor 4, carry out catalyzed reaction, catalyzer is arranged in the isomerization reactor 4 with the form of fixed bed, reactant flow is passed through fixed bed with liquid form; The isomerization reactor internal pressure is 3.5MPa, temperature of reaction is 400 ℃～410 ℃, step 2) and the bottom product Continuous Flow of step 3) cross fixed bed, isomerization reaction takes place under catalyst action, make part hemimellitene, the isomerization of sym-trimethylbenzene recurring structure and become unsym-trimethyl benzene, simultaneously, there is part o-methylethylbenzene isomery to become p-methyl-ethylbenzene and m-methyl ethylbenzene;
5) reaction product that step 4) is obtained constantly is input to lightness-removing column 1, sends in second rectifying tower 3 after taking off gently, and rectifying obtains unsym-trimethyl benzene in second rectifying tower 3, and bottom product is sent into again and carried out circulating reaction in the isomerization reactor 4.
The C9 aromatics isomerization is produced the method for unsym-trimethyl benzene, and step is as follows:
1) purity that will extract behind the sym-trimethylbenzene is taken off light processing more than or equal to 90% C9 aromatic hydrocarbons in lightness-removing column 1, the working temperature of control lightness-removing column 1 is 166 ℃～168 ℃, after making boiling point be lower than 166 ℃ o-methylethylbenzene, m-methyl ethylbenzene, p-methyl-ethylbenzene, sym-trimethylbenzene, n-proplbenzene and isopropyl benzene vaporization and leaving lightness-removing column 1 from cat head, enter first rectifying tower 2; The boiling point that keeps at the bottom of the tower of lightness-removing column 1 is higher than 168 ℃ unsym-trimethyl benzene and hemimellitene and is delivered to second rectifying tower 3;
2) in second rectifying tower 3, rectification temperature is 169.5 ℃～175 ℃, and unsym-trimethyl benzene leaves and is collected from second rectifying tower, 3 tops, and second rectifying tower, 3 bottoms keep hemimellitene;
3) in first rectifying tower 2, rectification temperature is 162 ℃～164 ℃, keeps sym-trimethylbenzene and o-methylethylbenzene at the bottom of the tower;
4) with above-mentioned steps 2) and the bottom product of step 3) send into simultaneously in the airtight isomerization reactor 4, carry out catalyzed reaction, catalyzer is arranged in the isomerization reactor 4 with the form of fixed bed, reactant flow is passed through fixed bed with liquid form; The isomerization reactor internal pressure is 3MPa, temperature of reaction is 300 ℃, step 2) and the bottom product Continuous Flow of step 3) cross fixed bed, isomerization reaction takes place under catalyst action, make part hemimellitene, the isomerization of sym-trimethylbenzene recurring structure and become unsym-trimethyl benzene, simultaneously, there is part o-methylethylbenzene isomery to become p-methyl-ethylbenzene and m-methyl ethylbenzene;
5) reaction product that step 4) is obtained constantly is input to lightness-removing column 1, sends in second rectifying tower 3 after taking off gently, and rectifying obtains unsym-trimethyl benzene in second rectifying tower 3, and bottom product is sent into again and carried out circulating reaction in the isomerization reactor 4.
Embodiment 4
Difference from Example 1 is that the isomerization reactor internal pressure is 1.5～2MPa, and temperature of reaction is 350 ℃.
The fundamental diagram of above-described embodiment 1～4, as shown in Figure 1.
The C9 aromatics isomerization is produced the method for unsym-trimethyl benzene, comprises the steps:
1) purity is taken off light processing more than or equal to 90% C9 aromatic hydrocarbons in lightness-removing column 1, the working temperature of control lightness-removing column 1 is 166 ℃～168 ℃, after making boiling point be lower than 166 ℃ o-methylethylbenzene, m-methyl ethylbenzene, p-methyl-ethylbenzene, sym-trimethylbenzene, n-proplbenzene and isopropyl benzene vaporization and leaving lightness-removing column 1 from cat head, enter first rectifying tower 2; The boiling point that keeps at the bottom of the tower of lightness-removing column 1 is higher than 168 ℃ unsym-trimethyl benzene and hemimellitene and is delivered to second rectifying tower 3;
2) in second rectifying tower 3, rectification temperature is 169.5 ℃～175 ℃, and unsym-trimethyl benzene leaves and is collected from second rectifying tower, 3 tops, and second rectifying tower, 3 bottoms keep hemimellitene;
3) in first rectifying tower 2, rectification temperature is 162 ℃～164 ℃, keeps sym-trimethylbenzene and o-methylethylbenzene at the bottom of the tower;
4) with above-mentioned steps 2) and the bottom product of step 3) send into simultaneously in the airtight isomerization reactor 4, carry out catalyzed reaction, catalyzer is arranged in the isomerization reactor 4 with the form of fixed bed, reactant flow is passed through fixed bed with liquid form; The isomerization reactor internal pressure is 0.5MPa, temperature of reaction is 280 ℃, step 2) and the bottom product Continuous Flow of step 3) cross fixed bed, isomerization reaction takes place under catalyst action, make part hemimellitene, the isomerization of sym-trimethylbenzene recurring structure and become unsym-trimethyl benzene, simultaneously, there is part o-methylethylbenzene isomery to become p-methyl-ethylbenzene and m-methyl ethylbenzene;
5) isomerization reaction product that step 4) is obtained is input to the 3rd rectifying tower 5, in the 3rd rectifying tower 5,166 ℃～168 ℃ of rectification temperatures make the isomerization product of sym-trimethylbenzene, o-methylethylbenzene and o-methylethylbenzene leave from the top of the 3rd rectifying tower 5, and circulation enters in the isomerization reactor 4; The unsym-trimethyl benzene and the hemimellitene that keep at the bottom of the tower of the 3rd rectifying tower 5 are sent in the 4th rectifying tower 6, the rectification temperature of the 4th rectifying tower 6 is 169.5 ℃～175 ℃, unsym-trimethyl benzene leaves and is collected from the 4th rectifying tower 6 tops, and the hemimellitene that the 4th rectifying tower 6 bottoms keep circulates again and enters in the isomerization reactor 4.
Difference from Example 5 is that the isomerization reactor internal pressure is 2.5MPa, and temperature of reaction is 380 ℃.
Embodiment 7
Difference from Example 5 is that the isomerization reactor internal pressure is 2MPa, and temperature of reaction is 320 ℃.
Embodiment 8
Difference from Example 5 is that the isomerization reactor internal pressure is 0.5MPa, and temperature of reaction is 300 ℃.
The principle of work of above-described embodiment 5～8 as shown in Figure 2.
Through some verification experimental verifications, can obtain temperature and productive rate table in the following isomerization reactor
| Temperature (℃) | Selectivity % | Productive rate % |
| 260 | 23 | 33 |
| 280 | 25 | 36 |
| 300 | 28 | 38 |
| 320 | 35 | 41 |
| 340 | 37 | 42 |
| 360 | 42 | 44 |
| 380 | 41 | 43 |
| 410 | 40 | 40 |
Through some verification experimental verifications, can obtain pressure and productive rate table in the following isomerization reactor
| Pressure (Mpa) | Selectivity % | Productive rate % |
| 0.2 | 52 | 38 |
| 0.5 | 47 | 35 |
| 1 | 44 | 33 |
| 1.5 | 38 | 30 |
| 2 | 40 | 28 |
| 2.5 | 42 | 27 |
| 3 | 45 | 26 |
| 3.5 | 45 | 25 |
Can get through a large amount of tests, with the rising of temperature, the productive rate of unsym-trimethyl benzene is also rising, but when temperature was lower than 260 ℃, isomerization reaction was carried out very slowly, and the productive rate of unsym-trimethyl benzene is very low, and when temperature was below 180 ℃, isomerization reaction can not be carried out; When temperature was higher than 410 ℃, other by products that reaction generates were more, cause the productive rate of unsym-trimethyl benzene also very low, so the suitable value of the temperature range in the isomerization reactor is 260 ℃～410 ℃.The variation of the pressure in the isomerization reaction container is less relatively to the influence of isomerization reaction, but too high pressure is had relatively high expectations to reaction vessel, and low excessively reaction pressure can cause the flow velocity of gas turnover to reduce, and is not easy to produce, therefore, the pressure optimum range is 0.2～3.5Mpa.
Embodiment 9
In above-described embodiment 1～8, catalyzer can obtain by the following method, it is 11 zeolite that the catalysagen material package is drawn together water, water glass, Tai-Ace S 150, silica alumina ratio, raw material mixes the back and forms colloid, becoming the glue temperature is 75 ℃, time is 2 hours, crystallization temperature is 220 ℃, crystallization time is 8 hours, obtains synthetic zeolite, and synthetic zeolite is passed through ion-exchange removal part A l atom wherein again, the mol ratio that makes silicon and aluminium is 40, sodium is taken off in washing again, and it is 80% that the sodium degree is taken off in control, and high-temperature roasting obtains pulverous catalyzer then.
The carrier of described catalyzer is aluminum oxide, and described aluminum oxide and catalyzer, water, mineral binder bond are mixed into paste, extrusion moulding on banded extruder again, after the moulding in 110～150 ℃ of down oven dry, activated again after, place in the fixed bed; The carrier consumption is 10～50% of all solids thing (catalyzer, aluminum oxide and mineral binder bond, down together) weight; Mineral binder bond is at least a in water glass, aluminum phosphate, calcium oxide, magnesium oxide and the calcium sulfate.
Embodiment 10
In above-described embodiment 1～8, catalyzer can obtain by the following method, it is 8 zeolite that the catalysagen material package is drawn together water, water glass, Tai-Ace S 150, silica alumina ratio, raw material mixes the back and forms colloid, becoming the glue temperature is 40 ℃, time is 2 hours, crystallization temperature is 150 ℃, crystallization time is 8 hours, obtains synthetic zeolite, and synthetic zeolite is passed through ion-exchange removal part A l atom wherein again, the mol ratio that makes silicon and aluminium is 10, sodium is taken off in washing again, and it is 20% that the sodium degree is taken off in control, and high-temperature roasting obtains pulverous catalyzer then.
The carrier of described catalyzer is aluminum oxide, and described aluminum oxide and catalyzer, water, mineral binder bond are mixed into paste, extrusion moulding on banded extruder again, after the moulding in 110 ℃ of down oven dry, activated again after, place in the fixed bed; The carrier consumption is 10% of all solids thing weight; Mineral binder bond is water glass.
Embodiment 11
In above-described embodiment 1～8, catalyzer can obtain by the following method, it is 12 zeolite that the catalysagen material package is drawn together water, water glass, Tai-Ace S 150, silica alumina ratio, raw material mixes the back and forms colloid, becoming the glue temperature is 75 ℃, time is 10 hours, crystallization temperature is 220 ℃, crystallization time is 20 hours, obtains synthetic zeolite, and synthetic zeolite is passed through ion-exchange removal part A l atom wherein again, the mol ratio that makes silicon and aluminium is 150, sodium is taken off in washing again, and it is 90% that the sodium degree is taken off in control, and high-temperature roasting obtains pulverous catalyzer then.
The carrier of described catalyzer is aluminum oxide, and described aluminum oxide and catalyzer, water, mineral binder bond are mixed into paste, extrusion moulding on banded extruder again, after the moulding in 150 ℃ of down oven dry, activated again after, place in the fixed bed; The carrier consumption is 50% of all solids thing weight; Mineral binder bond is aluminum phosphate and the calcium oxide of any weight ratio.
Embodiment 12
In above-described embodiment 1～8, catalyzer can obtain by the following method, it is 10 zeolite that the catalysagen material package is drawn together water, water glass, Tai-Ace S 150, silica alumina ratio, raw material mixes the back and forms colloid, becoming the glue temperature is 55 ℃, time is 6 hours, crystallization temperature is 180 ℃, crystallization time is 14 hours, obtains synthetic zeolite, and synthetic zeolite is passed through ion-exchange removal part A l atom wherein again, the mol ratio that makes silicon and aluminium is 80, sodium is taken off in washing again, and it is 55% that the sodium degree is taken off in control, and high-temperature roasting obtains pulverous catalyzer then.The carrier of described catalyzer is aluminum oxide, and described aluminum oxide and catalyzer, water, mineral binder bond are mixed into paste, extrusion moulding on banded extruder again, after the moulding in 130 ℃ of down oven dry, activated again after, place in the fixed bed; The carrier consumption is 30% of all solids thing weight; Mineral binder bond is calcium oxide, magnesium oxide and the calcium sulfate of any weight ratio.
Embodiment 13
In above-described embodiment 1～8, catalyzer can obtain by the following method, it is 9 zeolite that described catalysagen material package is drawn together water, water glass, Tai-Ace S 150, silica alumina ratio, raw material mixes the back and forms colloid, becoming the glue temperature is 65 ℃, time is 4 hours, crystallization temperature is 200 ℃, crystallization time is 10 hours, obtains synthetic zeolite, and synthetic zeolite is passed through ion-exchange removal part A l atom wherein again, the mol ratio that makes silicon and aluminium is 120, sodium is taken off in washing again, and it is 30% that the sodium degree is taken off in control, and high-temperature roasting obtains pulverous catalyzer then.
Embodiment 14
The method that described catalyzer is not limited to above-described embodiment 9～13 obtains, described catalysagen material package is drawn together water, water glass, Tai-Ace S 150, silica alumina ratio can be 8～12 zeolite, raw material mixes the back and forms colloid, become the glue temperature to can be 40～75 ℃, time can be 2～10 hours, crystallization temperature can be 150～220 ℃, crystallization time is 8～20 hours, obtain synthetic zeolite, again through ion-exchange removal part A l atom wherein, the mol ratio that makes silicon and aluminium is 10～150 with synthetic zeolite, and sodium is taken off in washing again, it is 20～90% that the sodium degree is taken off in control, and high-temperature roasting obtains pulverous catalyzer then.
The carrier of catalyzer is aluminum oxide, and aluminum oxide and catalyzer, water, mineral binder bond are mixed into paste, extrusion moulding on banded extruder again, after the moulding in 110～150 ℃ of down oven dry, activated again after, place in the fixed bed; Described carrier consumption be outside dewatering all solids thing weight 10～50%.Mineral binder bond is a kind of in water glass, aluminum phosphate, calcium oxide, magnesium oxide and the calcium sulfate or several.
The present invention is not limited to above-described embodiment; on the basis of technical scheme disclosed by the invention; those skilled in the art is according to disclosed technology contents; do not need performing creative labour just can make some replacements and distortion to some technical characterictics wherein, these replacements and distortion are all in protection scope of the present invention.
Claims (7)
1.C9 aromatics isomerization is produced the method for unsym-trimethyl benzene, it is characterized in that comprising the steps:
1) purity is taken off light processing more than or equal to 90% C9 aromatic hydrocarbons in lightness-removing column, the working temperature of control lightness-removing column is 166 ℃～168 ℃, after making boiling point be lower than 166 ℃ o-methylethylbenzene, m-methyl ethylbenzene, p-methyl-ethylbenzene, sym-trimethylbenzene, n-proplbenzene and isopropyl benzene vaporization and leaving lightness-removing column from cat head, enter first rectifying tower; The boiling point that keeps at the bottom of the tower of lightness-removing column is higher than 168 ℃ unsym-trimethyl benzene and hemimellitene and is delivered to second rectifying tower;
2) in second rectifying tower, rectification temperature is 169.5 ℃～175 ℃, and unsym-trimethyl benzene leaves and is collected from the second rectifying tower top, and second rectifier bottoms keeps hemimellitene;
3) in first rectifying tower, rectification temperature is 162 ℃～164 ℃, keeps sym-trimethylbenzene and o-methylethylbenzene at the bottom of the tower;
4) with above-mentioned steps 2) and the bottom product of step 3) send into simultaneously in the airtight isomerization reactor, carry out catalyzed reaction, catalyzer is arranged in the isomerization reactor with the form of fixed bed, reactant flow is passed through fixed bed with liquid form; The isomerization reactor internal pressure is 0.2MPa～3.5MPa, temperature of reaction is 260 ℃～410 ℃, step 2) and the bottom product Continuous Flow of step 3) cross fixed bed, isomerization reaction takes place under catalyst action, make part hemimellitene, the isomerization of sym-trimethylbenzene recurring structure and become unsym-trimethyl benzene, simultaneously, there is part o-methylethylbenzene isomery to become p-methyl-ethylbenzene and m-methyl ethylbenzene;
5) with above-mentioned steps 4) reaction product again rectifying obtain unsym-trimethyl benzene.
2. C9 aromatics isomerization according to claim 1 is produced the method for unsym-trimethyl benzene, it is characterized in that described step 5) is by constantly being input to described lightness-removing column with isomerization reaction product, after taking off gently, send in described second rectifying tower, rectifying obtains unsym-trimethyl benzene in second rectifying tower, and bottom product is sent into again and carried out circulating reaction in the isomerization reactor.
3. C9 aromatics isomerization according to claim 1 is produced the method for unsym-trimethyl benzene, it is characterized in that described step 5) is by isomerization reaction product being input to the 3rd rectifying tower, in the 3rd rectifying tower, 166 ℃～168 ℃ of rectification temperatures, the isomerization product of sym-trimethylbenzene, o-methylethylbenzene and o-methylethylbenzene is left from the top of the 3rd rectifying tower, and circulation enter in the isomerization reactor; The unsym-trimethyl benzene and the hemimellitene that keep at the bottom of the tower of the 3rd rectifying tower are sent in the 4th rectifying tower, the rectification temperature of the 4th rectifying tower is 169.5 ℃～175 ℃, unsym-trimethyl benzene leaves and is collected from the 4th rectifying tower top, and the hemimellitene that the 4th rectifier bottoms keeps circulates again and enters in the isomerization reactor.
4. according to any method that described C9 aromatics isomerization is produced unsym-trimethyl benzene of claim 1～3, it is characterized in that described catalysagen material package draws together water, water glass, Tai-Ace S 150, silica alumina ratio is 8～12 zeolite, raw material mixes the back and forms colloid, becoming the glue temperature is 40～75 ℃, time is 2～10 hours, crystallization temperature is 150～220 ℃, crystallization time is 8～20 hours, obtain synthetic zeolite, again through ion-exchange removal part A l atom wherein, the mol ratio that makes silicon and aluminium is 10～150 with synthetic zeolite, and sodium is taken off in washing again, it is 20～90% that the sodium degree is taken off in control, and high-temperature roasting obtains pulverous catalyzer then.
5. C9 aromatics isomerization according to claim 4 is produced the method for unsym-trimethyl benzene, it is characterized in that described catalyzer is carrier with the aluminum oxide in addition, described aluminum oxide and catalyzer, water, mineral binder bond are mixed into paste, extrusion moulding on banded extruder again, dry down in 110～150 ℃ after the moulding, behind high-temperature activation, place in the fixed bed again.
6. C9 aromatics isomerization according to claim 5 is produced the method for unsym-trimethyl benzene, it is characterized in that described carrier consumption is 10～50% of all solids thing weight.
7. C9 aromatics isomerization according to claim 6 is produced the method for unsym-trimethyl benzene, it is characterized in that described mineral binder bond is at least a in water glass, aluminum phosphate, calcium oxide, magnesium oxide and the calcium sulfate.
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| KR101970761B1 (en) | 2018-12-05 | 2019-04-22 | 부경대학교 산학협력단 | 1,2,4-Trimethylbenzene separation equipment using extractive distillation and separation method with the equipment |
| DE212021000103U1 (en) * | 2021-06-24 | 2021-08-03 | Pengchen New Material Technology Co., Ltd. | A rectifier for the production of 1,2,4-trimethylbenzene |
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