CN101768039B - Method for lightening and transalkylation of C9 and heavier aromatic hydrocarbons - Google Patents
Method for lightening and transalkylation of C9 and heavier aromatic hydrocarbons Download PDFInfo
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- CN101768039B CN101768039B CN200910056810A CN200910056810A CN101768039B CN 101768039 B CN101768039 B CN 101768039B CN 200910056810 A CN200910056810 A CN 200910056810A CN 200910056810 A CN200910056810 A CN 200910056810A CN 101768039 B CN101768039 B CN 101768039B
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Abstract
The invention relates to a method for lightening and transalkylation of C9 and heavier aromatic hydrocarbons. The method mainly solves the technical problems that the conversion rate of the heavier aromatic hydrocarbons and the selectivity of object products are low, ring opening of aromatic rings is serious, and a catalyst needs to load noble metals in the prior art when the C9 and the heavier aromatic hydrocarbons is processed to increase the yield of benzene, methylbenzene and dimethyl benzene. The method adopts the technical scheme that: raw materials such as the C9 and the heavier aromatic hydrocarbons contact a catalyst through a fixed bed reactor, wherein the reaction temperature is between 250 and 600 DEG C; the reaction pressure is between 1.0 and 5.0 MPa; the raw material weight space velocity is between 0.5 and 10.0 per hour; the mole ratio of hydrogen to hydrocarbon is 0.5-6.0:1; and the catalyst comprises the following components in part by weight: 20 to 90 parts of hydrogenous nano-zeolite of which the mole ratio of SiO2 to Al2O3 is 8 to 200, and 10 to 80 parts of agglomerant. The method for the lightening and the transalkylation of the C9 and heavier aromatic hydrocarbons can preferably solve the problems and can be used for industrial production of the lightening and the transalkylation of the heavier aromatic hydrocarbons.
Description
Technical field
The present invention relates to a kind of method that is used for carbon nine and above heavy aromatic hydrocarbon light and transalkylation; Particularly about being raw material with carbon nine and above heavy arene thereof; Use the catalyzer that does not need carried noble metal, through the method for lighting and transalkylation process raising the output benzene,toluene,xylene.
Background technology
Nanoparticle has tangible volume effect, surface effects and quantum size effect; Nano zeolite is owing to have bigger external surface area and a higher intracrystalline rate of diffusion, in the utilization ratio that improves catalyzer, strengthen the macromole conversion capability, reduce deep reaction, improve selectivity and reduce aspects such as coking and deactivation and all show superior performance.
Heavy arene (or heavy aromatics) refers to the carbon nine above aromatic hydrocarbons of by-product in the oil and the coal course of processing, is mainly derived from the sub product that light oil cracking is produced ethylene unit; The extracting aromatic hydrocarbons of refinery CR; The wide fraction catalytic reforming unit by-product C of polyester raw material factory
10(carbon ten) heavy aromatics; The sub product of toluene disproportionation and transalkylation unit; Ethylene unit by-product ethylene bottom oil.Along with the increase of oil-refining capacity, the construction in the large-scale ethylene production of MT base and the maximization of Aromatic Hydrocarbon United Plant, heavy aromatics output is considerable.Comprehensive Utilization of Heavy Aromatics is the problem that people are concerned about, wherein C
9The processing and utilization of A (C9 aromatic) has sophisticated method, generally as the raw material of toluene disproportionation and transalkylation reaction, is used for making benzene and YLENE.C
10The composition of heavy aromatics is very complicated, and 100 various ingredients are arranged altogether approximately.The component that wherein economic worth is bigger only contains about 8%.These components are all improper as the blend composition of gasoline or diesel oil, generally pass through simple distillation operation, isolate durol (196.1 ℃ of boiling points; 73.4 ℃ of fusing points), isodurene (boiling point 197.8; Fusing point-23.9), naphthalene (217.8 ℃ of boiling points), methylnaphthalene (241.1～244.4 ℃ of boiling points, 30.5～34.9 ℃ of fusing points) etc., a part is as producing serial solvent oil; All the other big is used as fuel, 20%～30% C is arranged simultaneously
10Heavy aromatics is converted into heavy oil residue, and raw material availability is low.Both wasted resource, also serious environment pollution damages HUMAN HEALTH.According to existing C
10The production and operation pattern of heavy aromatics is difficult to bring into play C
10The due economic benefit of heavy aromatics resource also will directly influence the normal operation of each big Aromatic Hydrocarbon United Plant simultaneously.Heavy aromatics is a kind of resource of preciousness, and present Aromatic Hydrocarbon United Plant is to C
10A fraction heavy aromatics does not also have the proper process method.
Because benzene and YLENE all are main basic organic, purposes is wider relatively, and price is also higher relatively, and toluene is important Organic Chemicals, therefore, utilizes C
9Above heavy aromatic hydrocarbon light and transalkylation reaction are produced benzene, toluene and YLENE and have been received people's attention, can increase economic efficiency, and cut the waste, and also help protecting environment.
With toluene and heavy aromatics is that raw material is produced benzene and YLENE, its production approach, nothing more than following three kinds:
First kind is that mixture with toluene and an amount of heavy aromatics is a raw material, comes processing through toluene disproportionation and transalkylation process, and this method has been traditional technological process.Heavy aromatics content can reach 40～50% (weight) at most in this raw materials technology, and 95% (weight) all is C in the heavy aromatics that is mentioned
9A, heavy aromatics be the C of relative low price particularly
10 +Hydrocarbon (carbon ten and above hydrocarbon thereof) is not utilized effectively.Toluene and C
9The content sum of A aromatic hydrocarbons requires in 97% (weight) or higher scope, and C
10The content of A is merely 3% (weight) or lower, and transformation efficiency is on the low side, about 80% C
10Heavy aromatics is discharged at the bottom of the heavy aromatics Tata.
Second kind of technological process is to obtain the purpose product through heavy aromatic hydrocarbon light fully.
The third technology is to be the selective disproportionation technology of raw material production benzene and highly selective p-Xylol with the pure toluene.This technology is active constituent with the silicon modified ZSM-5 zeolite mainly, can not handle heavy aromatics.
The heavy aromatics hydrodealkylation catalyst mainly divides two types at present, and one type is metal oxide catalyst, and another kind of is sieve catalyst.
Metal oxide catalyst mainly is chromic oxide (Cr
2O
3) and molybdenum oxide (MoO
3) catalyzer, adopting this type catalyzer desired reaction temperature high (about 570～650 ℃), reaction pressure is big, and side reaction is many, and air speed is low.As opening the spy in the clear 51-29131 patent, use MoO
3-NiO/Al
2O
3(13% weight Mo, 5% weight Ni) catalyzer is with C
9A～C
10(weight percent consists of A: benzene 0.81%, toluene 0.26%, C
8A (C8 aronmatic) 0.95%, C
9A 80.96%, C
10A 15.23%) be raw material, reaction under 6MPa and 550 ℃ of reaction conditionss, during reaction product is formed by weight percentage for containing benzene 9.74%, toluene 30.27%, YLENE 32.33% and non-aromatic hydrocarbons 0.16%.
Adopting the sieve catalyst desired reaction temperature is low than metal oxide catalyst, helps avoiding catalyst deactivation.
In USP4172813,3%WO by weight percentage
3, 5%MoO
3-60% mordenite-40%Al
2O
3Be catalyzer, make heavy reformate generation hydro-dealkylation and transalkylation reaction.Its temperature of reaction is 315～538 ℃, and reaction pressure is 150～500Psig, and reaction raw materials contains non-aromatic hydrocarbons 0.5%, C
8A 0.4%, toluene 28.3%, and trimethylbenzene 46.6%, the first and second benzene 11.6%, indane adds propyl benzene 2.1%, durene 10.1%, C
10Above aromatic hydrocarbons 0.4%.Raw material only contains C in forming
10A10.1% contains 28.3% toluene, 46.6% trimethylbenzene.
In USP 4341622, be catalyzer with the restricted index 1～12 of carried noble metal, high silica alumina ratio, low tart zeolite, make heavy reformate generation hydro-dealkylation and transalkylation reaction.Its temperature of reaction is 427～540 ℃.
In USP 5001296, be catalyzer with the MCM-22 zeolite of carried noble metal, can be benzene, toluene and YLENE (BTX) 315～482 ℃ of feedstock conversion with C9A content 96.8% (mole).
In CN 1117404, be catalyzer with the ZSM-5 of carried noble metal, at 350～450 ℃ with C
9The feedstock conversion of A content 97.95% (weight) is BTX, C
9The A transformation efficiency is in 22.9～64.3% (weight).
In CN 1270989 and CN 1472181, the ZSM-5/ mordenite composite molecular sieve with carried noble metal is a catalyzer respectively, at 350～450 ℃ with C
9The feedstock conversion of A content 97.95% (weight) is BTX, C
9The A transformation efficiency is in 32.3～41.91% (weight).
In CN 1472182, the ZSM-5/ β zeolite composite molecular screen with carried noble metal is a catalyzer respectively, at 350～450 ℃ with C
9The feedstock conversion of A content 97.95% (weight) is BTX, C
9The A transformation efficiency is in 32.3～46% (weight).
In CN 101045208, be catalyzer with β zeolite, mordenite, ZSM-5 or the ZSM-12 that carries palladium, at 375 ℃ with C
9 +A, toluene reach or benzene is recycle feed, and transformation efficiency is between 65～75%.
In CN 1850337, to use through the nanometer HZSM-5 zeolite catalyst after the three step modifications, toluene and trimethylbenzene are that raw material carries out transalkylation reaction; The above heavy aromatics processing power of C10 is low; X/B is merely 1.7～2.0 in the product, and purpose product YLENE yield is low, is unfavorable for increasing economic efficiency.
In CN 1752058, be catalyzer with the metal of load bismuth and molybdenum or the large pore zeolite of oxide compound, can handle the raw material that contains certain carbon 11 above aromatic hydrocarbons, but the C10 aromartic transformation efficiency is lower.
Need carried noble metal in the above-mentioned document mostly; Increased the catalyzer cost; All contain a large amount of toluene in the raw material that uses simultaneously; Heavy aromatics, the particularly processing power of the above heavy aromatics of C10 are weak, the heavy arene transformation efficiency is low, the purpose product yield is low, the aromatic ring open loop is serious, catalyzer needs carried noble metal and poor stability, thereby limited its industrializing implementation.
Summary of the invention
Technical problem to be solved by this invention is to be raw material in order to overcome what exist in the prior art with carbon nine and above heavy arene thereof; When preparing benzene,toluene,xylene through lighting and transalkylation process; The technical problem that the heavy arene transformation efficiency is low, the purpose product selectivity is low, the aromatic ring open loop serious, catalyzer needs carried noble metal provides a kind of new method that is used for carbon nine and above heavy aromatic hydrocarbon light and transalkylation.This method has, and can to adopt pure heavy aromatics be raw material; Can effectively carbon nine and above heavy arene thereof be taken off alkyl and transalkylation reaction; Generate a large amount of useful benzene, toluene and YLENE products; Have the catalyst activity height, the heavy arene treatment capacity is big, benzene, toluene and the high characteristics of C8 aronmatic selectivity of product.
For solving the problems of the technologies described above; The technical scheme that the present invention adopts is following: a kind of method that is used for carbon nine and above heavy aromatic hydrocarbon light and transalkylation is a raw material with carbon nine and above heavy arene thereof, and raw material passes through fixed-bed reactor; Contact with catalyzer; In temperature of reaction is 250～600 ℃, and reaction pressure is 0.5～5.0MPa, and the raw material weight air speed is 0.5～10.0 hour
-1, hydrogen/hydrocarbon mol ratio is to carry out hydro-dealkylation and transalkylation under 0.5～6.0: 1 the condition, generates carbon six～C8 aronmatic, wherein used catalyzer comprises 20～90 parts of SiO in parts by weight
2/ Al
2O
3Mol ratio is 8～200 Hydrogen nano zeolite and 10～80 parts sticker.
In the technique scheme, the temperature of reaction preferable range is 300～550 ℃, and the reaction pressure preferable range is 0.5～4.5MPa, and raw material weight air speed preferable range is 1.0～10.0 hours
-1, hydrogen/hydrocarbon mol ratio preferable range is 0.5～6.0: 1.Described carbon six～C8 aronmatic comprises benzene,toluene,xylene and ethylbenzene.
In the technique scheme, the Hydrogen nano zeolite is selected from least a among β zeolite, mordenite, the ZSM-5.Sticker is selected from aluminum oxide, pseudo-boehmite, silicon-dioxide, oxidation sial, wilkinite, kaolin, zeyssatite or the smectite at least a.The Hydrogen nano zeolite is preferentially selected β zeolite, mordenite or its mixture for use, and the particle diameter of nano zeolite is 5～100nm.The SiO of Hydrogen nanometer β zeolite
2/ Al
2O
3Mol ratio is 15～200, the SiO of Hydrogen nano mordenite
2/ Al
2O
3Mol ratio is 8～70, and Hydrogen nanometer β zeolite and Hydrogen nano mordenite can mix by arbitrary proportion.Used catalyzer preferred version is also to comprise group vib metal or its oxide compound in the catalyzer, and the weight ratio of its consumption and Hydrogen nano zeolite is 0.001～0.5: 1.
In the technique scheme, Hydrogen nano zeolite priority scheme is selected from β zeolite, mordenite or its mixture, and some scopes of the particle diameter of nano zeolite are 20～100nm.The sticker preferred version is selected from aluminum oxide, pseudo-boehmite, silicon-dioxide, the kaolin at least a.The weight ratio preferable range of group vib metal or its oxide compound and Hydrogen nano zeolite is 0.005～0.3: 1.
In the technique scheme, raw material is selected from carbon nine and above heavy arene thereof or in heavy arene, adds toluene or benzene.Reaction product can be circulated in the reaction feed through the carbon nine and the above aromatic hydrocarbons thereof of the isolated carbon seven of deheptanizer and following hydrocarbon and YLENE Tata still.
The present invention is to provide a kind of method that is used for carbon nine and above heavy aromatic hydrocarbon light and transalkylation, is raw material with carbon nine and above heavy arene thereof, and raw material contacts with catalyzer through fixed-bed reactor, can be used for preparing carbon six～C8 aronmatic.
Among the present invention owing to adopt nano zeolite, catalyzer acid position utilization ratio high, strength of acid and acid amount all are improved, and help the diffusion of reactant and product molecule.Behind group vib metal or its oxide modifying, the catalytic performance of nano zeolite has had further raising.Adopt method provided by the invention, being used for heavy arene is that raw material carries out lighting and transalkylation reaction, and 250～600 ℃ of temperature, reaction pressure is 0.5～3.0MPa, and the raw material weight air speed is 0.5～10.0 hour
-1, hydrogen/hydrocarbon mol ratio is that transformation efficiency can reach 71.66% under 0.5～6.0: 1 the condition, and selectivity can reach 79.60%, and the aromatic ring loss is reduced to 0.76%, has obtained better technical effect.
The present invention uses fixed-bed reactor to carry out reactivity worth and investigates 14 millimeters of reactor inside diameter φ, 500 millimeters of length, stainless steel.Adopt electrically heated, temperature is controlled automatically.5 millimeters granulated glass spherees of reactor bottom filling φ are as upholder, filling catalyzer 5 grams in the reactor drum, and 5 millimeters granulated glass spherees of top filling φ are made for the usefulness of raw material preheating and vaporization.Material carbon nine and above heavy arene thereof mix with hydrogen, from top to bottom through beds, lighting and transalkylation reaction take place, and generate more rudimentary aromatic hydrocarbons such as benzene, ethylbenzene, YLENE, and alkane such as a small amount of methane, ethane, propane, butane.
Material carbon nine and above heavy arene (C thereof
9 +A) derive from the petrochemical complex Aromatic Hydrocarbon United Plant, testing data is calculated as follows.
Through embodiment the present invention is done further elaboration below, but therefore do not limit protection scope of the present invention.
Embodiment
[embodiment 1]
Get Na
2O content is less than 0.10% (weight), SiO
2/ Al
2O
3Nanometer β zeolite 55 grams and the Na of mol ratio 20.5, particle diameter 80～100nm
2O content less than 0.15%, pseudo-boehmite 45 grams and the 1 gram extrusion aid sesbania powder of calcination loss 30% mix; Add 1.5 milliliters in CP nitric acid, 60 milliliters of deionized waters; Thorough mixing, kneading are evenly; Carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, and made catalyst A.
[embodiment 2]
Get Na
2O content is less than 0.10% (weight), SiO
2/ Al
2O
3Nanometer β zeolite 60 grams and the Na of mol ratio 62.4, particle diameter 20～40nm
2O content less than 0.15%, pseudo-boehmite 45 grams and the 1 gram extrusion aid sesbania powder of calcination loss 30% mix; Add 1.5 milliliters in CP nitric acid, 60 milliliters of deionized waters; Thorough mixing, kneading are evenly; Carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, and made catalyst B.
[embodiment 3]
Get Na
2O content is less than 0.10% (weight), SiO
2/ Al
2O
3Nanometer β zeolite 65 grams and the Na of mol ratio 188, particle diameter 60～80nm
2O content less than 0.15%, pseudo-boehmite 45 grams and the 1 gram extrusion aid sesbania powder of calcination loss 30% mix; Add 1.5 milliliters in CP nitric acid, 60 milliliters of deionized waters; Thorough mixing, kneading are evenly; Carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, and made catalyzer C.
[embodiment 4]
Get Na
2O content is less than 0.10% (weight), SiO
2/ Al
2O
3Nano mordenite 70 grams and the Na of mol ratio 9.8, particle diameter 80～100nm
2O content is less than γ-Al of 0.15%
2O
330 grams and 5 gram extrusion aid sesbania powder mix, and add 1.5 milliliters in CP nitric acid, 60 milliliters of deionized waters, thorough mixing, mediate evenly, carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, make catalyzer D.
[embodiment 5]
Get Na
2O content is less than 0.10% (weight), SiO
2/ Al
2O
3Nano mordenite 70 grams and the Na of mol ratio 45.6, particle diameter 40～60nm
2O content is less than α-Al of 0.15%
2O
3H
2O 55 gram and 5 gram extrusion aid sesbania powder mix, and add 1.5 milliliters in CP nitric acid, 60 milliliters of deionized waters, thorough mixing, mediate evenly, carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, make catalyzer E.
[embodiment 6]
Get Na
2O content is less than 0.10% (weight), SiO
2/ Al
2O
3Nano-ZSM-5 molecular sieve 70 grams and the Na of mol ratio 32, particle diameter 10～40nm
2O content mixes less than 0.15% kaolin 35 grams and 1 gram extrusion aid sesbania powder; Add 1.5 milliliters in CP nitric acid, 60 milliliters of deionized waters; Thorough mixing, mediate evenly, carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, make catalyzer F
[embodiment 7]
Get Na
2O content is less than 0.10% (weight), SiO
2/ Al
2O
3Nano-ZSM-5 molecular sieve 70 grams and the Na of mol ratio 32, particle diameter 30～50nm
2O content mixes less than 0.05% silicon-dioxide 40 grams and 1 gram extrusion aid sesbania powder; Add 1.5 milliliters in CP nitric acid, 60 milliliters of deionized waters; Thorough mixing, mediate evenly, carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, make catalyzer G.
[embodiment 8]
Get Na
2O content is less than 0.10% (weight), SiO
2/ Al
2O
3Nanometer β zeolite 49 grams and the SiO of mol ratio 20.5, particle diameter 80～100nm
2/ Al
2O
3Nano mordenite 21 grams and the Na of mol ratio 45.6, particle diameter 40～60nm
2O content less than 0.15%, pseudo-boehmite 50 grams and the 1 gram extrusion aid sesbania powder of calcination loss 30% mix; Add 2 milliliters in CP nitric acid, 60 milliliters of deionized waters; Thorough mixing, kneading are evenly; Carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, and made catalyzer H.
[embodiment 9]
Get Na
2O content is less than 0.10% (weight), SiO
2/ Al
2O
3Nanometer β zeolite 21 grams and the SiO of mol ratio 62.4, particle diameter 20～40nm
2/ Al
2O
3Nano mordenite 49 grams and the Na of mol ratio 45.6, particle diameter 40～60nm
2O content less than 0.15%, pseudo-boehmite 50 grams and the 1 gram extrusion aid sesbania powder of calcination loss 30% mix; Add 2 milliliters in CP nitric acid, 60 milliliters of deionized waters; Thorough mixing, kneading are evenly; Carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, and made catalyst I.
[comparative example 1]
Get Na
2O content is less than 0.10% (weight), SiO
2/ Al
2O
3β zeolite 55 grams and the Na of mol ratio 20.5, particle diameter 300～500nm
2O content less than 0.15%, pseudo-boehmite 45 grams and the 1 gram extrusion aid sesbania powder of calcination loss 30% mix; Add 1.5 milliliters in CP nitric acid, 60 milliliters of deionized waters; Thorough mixing, kneading are evenly; Carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, and made catalyzer X1.
[comparative example 2]
Get Na
2O content is less than 0.10% (weight), SiO
2/ Al
2O
3Conventional mordenite 70 grams and the Na of mol ratio 10.0, particle diameter 2 μ m
2O content is less than γ-Al of 0.15%
2O
330 grams and 5 gram extrusion aid sesbania powder mix, and add 1.5 milliliters in CP nitric acid, 60 milliliters of deionized waters, thorough mixing, mediate evenly, carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, make catalyzer X2.
[embodiment 10～18]
Catalyst A～I with embodiment 1～9 makes carries out heavy aromatic hydrocarbon light and the investigation of transalkylation reaction performance at fixed-bed reactor, and weight space velocity is 2.5 hours
-1, 440 ℃ of temperature of reaction, reaction pressure 3.0MPa, hydrogen and raw molecule are than 4.0, and raw material is formed as shown in table 1.Evaluation result is as shown in table 2.
Table 1 heavy aromatic hydrocarbon light and transalkylation reaction raw material are formed, % (weight)
| Title | Non-virtue | Benzene | Toluene | Ethylbenzene | YLENE | Indane | C 9Aromatic hydrocarbons | C 10 +Aromatic hydrocarbons |
| Content | 0.04 | 0.02 | 0.00 | 0.17 | 0.03 | 1.54 | 78.04 | 20.16 |
Table 2 heavy aromatic hydrocarbon light and transalkylation reaction result
| Embodiment | 10 | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 |
| The catalyzer numbering | A | B | C | D | E | F | G | H | I |
| The heavy arene transformation efficiency, % (weight) | 47.46 | 49.45 | 51.53 | 55.23 | 52.47 | 54.58 | 47.88 | 52.02 | 54.52 |
| The BTX selectivity, % (weight) | 79.60 | 76.78 | 73.25 | 69.49 | 60.22 | 57.23 | 50.25 | 74.35 | 68.73 |
| The ring loss, % (weight) | 0.95 | 1.07 | 1.36 | 1.28 | 1.51 | 1.67 | 1.75 | 1.34 | 1.67 |
[comparative example 3～4]
Catalyzer X1, X2 with Comparative Examples 1～2 makes carry out heavy aromatic hydrocarbon light and the investigation of transalkylation reaction performance at fixed-bed reactor, and weight space velocity is 2.5 hours
-1, 440 ℃ of temperature of reaction, reaction pressure 3.0MPa, hydrogen and raw molecule are than 4.0, and raw material is formed as shown in table 1.Evaluation result is as shown in table 3.
Table 3 heavy aromatic hydrocarbon light and transalkylation reaction result
| Comparative example | 3 | 4 |
| The catalyzer numbering | X1 | X2 |
| The heavy arene transformation efficiency, % (weight) | 36.40 | 38.28 |
| The BTX selectivity, % (weight) | 44.53 | 42.69 |
| The ring loss, % (weight) | 3.25 | 4.28 |
[embodiment 19]
Get Na
2O content is less than 0.10% (weight), SiO
2/ Al
2O
3Nanometer β zeolite 55 grams and the Na of mol ratio 20.5, particle diameter 50～80nm
2O content less than 0.15%, pseudo-boehmite 45 grams and the 1 gram extrusion aid sesbania powder of calcination loss 30% mix; With CP Ammonium Heptamolybdate [(NH
4)
6Mo
7O
24] 4.6 grams, 2 milliliters in CP nitric acid, 60 milliliters of wiring solution-formings of deionized water; The mixture thorough mixing, the kneading that add this solution nanometer β zeolite and pseudo-boehmite are even; Carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, and made catalyzer J.
[embodiment 20]
Get Na
2O content is less than 0.10% (weight), SiO
2/ Al
2O
3Nano mordenite 70 grams and the Na of mol ratio 9.8, particle diameter 80～100nm
2O content is less than γ-Al of 0.15%
2O
330 grams and 5 gram extrusion aid sesbania powder mix; With CP Ammonium Heptamolybdate [(NH
4)
6Mo
7O
24] 0.46 gram, 2 milliliters in CP nitric acid, 60 milliliters of wiring solution-formings of deionized water, add nano mordenite zeolite and γ-Al to this solution
2O
3The mixture thorough mixing, mediate evenly, carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, make catalyzer K.
[embodiment 21]
Get Na
2O content is less than 0.10% (weight), SiO
2/ Al
2O
3Nano-ZSM-5 molecular sieve 60 grams and the Na of mol ratio 32, particle diameter 10～40nm
2O content mixes less than 0.15% kaolin 45 grams and 1 gram extrusion aid sesbania powder; With CP ammonium tetramolybdate [(NH
4)
2Mo
4O
13] 1.82 grams, 1.5 milliliters in CP nitric acid, 60 milliliters of wiring solution-formings of deionized water; Add this solution nano-ZSM-5 molecular sieve and kaolinic mixture thorough mixing, mediate evenly; Carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, and made catalyzer L.
[embodiment 22]
Get Na
2O content is less than 0.10% (weight), SiO
2/ Al
2O
3Nanometer β zeolite 49 grams and the SiO of mol ratio 20.5, particle diameter 80～100nm
2/ Al
2O
3Nano mordenite 21 grams and the Na of mol ratio 45.6, particle diameter 40～60nm
2O content less than 0.15%, pseudo-boehmite 50 grams and the 1 gram extrusion aid sesbania powder of calcination loss 30% mix; With CP Ammonium Heptamolybdate [(NH
4)
6Mo
7O
24] 4.6 grams, 2 milliliters in CP nitric acid, 60 milliliters of wiring solution-formings of deionized water; The mixture thorough mixing, the kneading that add this solution nanometer β zeolite, nano mordenite and pseudo-boehmite are even; Carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, and made catalyzer M.
[embodiment 23]
Get Na
2O content is less than 0.10% (weight), SiO
2/ Al
2O
3Nanometer β zeolite 55 grams and the Na of mol ratio 20.5, particle diameter 50～80nm
2O content less than 0.15%, pseudo-boehmite 45 grams and the 1 gram extrusion aid sesbania powder of calcination loss 30% mix; With CP ammonium paratungstate [H
40N
10W
12O
41] 16.4 grams, 2 milliliters in CP nitric acid, 60 milliliters of wiring solution-formings of deionized water; The mixture thorough mixing, the kneading that add this solution nanometer β zeolite and pseudo-boehmite are even; Carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, and made catalyst n.
[embodiment 24]
Get Na
2O content is less than 0.10% (weight), SiO
2/ Al
2O
3Nanometer β zeolite 55 grams and the Na of mol ratio 20.5, particle diameter 50～80nm
2O content less than 0.15%, pseudo-boehmite 45 grams and the 1 gram extrusion aid sesbania powder of calcination loss 30% mix; With CP chromium nitrate [Cr (NO
3) 9H
2O] 7.7 grams, 2 milliliters in CP nitric acid, 60 milliliters of wiring solution-formings of deionized water; The mixture thorough mixing, the kneading that add this solution nanometer β zeolite and pseudo-boehmite are even; Carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, and made catalyzer O.
[embodiment 25～30]
Catalyzer J～O with embodiment 19～24 makes carries out heavy aromatic hydrocarbon light and the investigation of transalkylation reaction performance at fixed-bed reactor, and weight space velocity is 2.5 hours
-1, 380 ℃ of temperature of reaction, reaction pressure 3.0MPa, hydrogen and raw molecule are than 4.0, and raw material is formed as shown in table 1.Evaluation result is as shown in table 4.
Table 4 heavy aromatic hydrocarbon light and transalkylation reaction result
| Embodiment | 25 | 26 | 27 | 28 | 29 | 30 |
| The catalyzer numbering | J | K | L | M | N | O |
| The heavy arene transformation efficiency, % (weight) | 58.21 | 51.45 | 54.66 | 55.30 | 62.83 | 61.08 |
| The BTX selectivity, % (weight) | 72.18 | 78.77 | 76.38 | 69.92 | 72.87 | 75.42 |
| The ring loss, % (weight) | 1.23 | 1.16 | 1.36 | 1.47 | 1.78 | 1.65 |
[comparative example 5]
Get Na
2O content is less than 0.10% (weight), SiO
2/ Al
2O
3β zeolite 55 grams and the Na of mol ratio 20.5, particle diameter 300～500nm
2O content less than 0.15%, pseudo-boehmite 45 grams and the 1 gram extrusion aid sesbania powder of calcination loss 30% mix; Add 1.5 milliliters in CP nitric acid, 60 milliliters of deionized waters; Thorough mixing, mediate evenly, carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, flood with certain density palladium nitrate solution again; Oven dry back roasting makes catalyzer X3, wherein contains palladium 0.36%.
[comparative example 6]
Get Na
2O content is less than 0.10% (weight), SiO
2/ Al
2O
3Conventional mordenite 70 grams and the Na of mol ratio 10.0, particle diameter 2 μ m
2O content is less than γ-Al of 0.15%
2O
330 grams and 5 gram extrusion aid sesbania powder mix; Add 1.5 milliliters in CP nitric acid, 60 milliliters of deionized waters; Thorough mixing, mediate evenly, carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, flood with certain density palladium nitrate solution again; Oven dry back roasting makes catalyzer X4, wherein contains palladium 0.25%.
[comparative example 7～8]
Catalyzer X3, X4 with comparative example 5～6 makes carry out heavy aromatic hydrocarbon light and the investigation of transalkylation reaction performance at fixed-bed reactor, and weight space velocity is 2.5 hours
-1, 400 ℃ of temperature of reaction, reaction pressure 3.0MPa, hydrogen/hydrocarbon molecule are than 4.0, and raw material is formed as shown in table 1.Evaluation result is as shown in table 5.
Table 5 heavy aromatic hydrocarbon light and transalkylation reaction result
| Comparative example | 7 | 8 |
| The catalyzer numbering | X3 | X4 |
| The heavy arene transformation efficiency, % (weight) | 39.60 | 42.84 |
| The BTX selectivity, % (weight) | 66.78 | 67.35 |
| The ring loss, % (weight) | 5.40 | 5.94 |
[embodiment 31～35]
Catalyzer J with embodiment 19 makes carries out heavy aromatic hydrocarbon light and the investigation of transalkylation reaction performance at fixed-bed reactor, and raw material is formed as shown in table 1.Evaluation result is as shown in table 6.
Table 6 heavy aromatic hydrocarbon light and transalkylation reaction result
| Embodiment | 25 | 31 | 32 | 33 | 34 | 35 |
| Temperature of reaction, ℃ | 380 | 320 | 500 | 400 | 420 | 460 |
| Weight space velocity, hour -1 | 2.5 | 1.0 | 4.0 | 8.0 | 2.5 | 3.0 |
| Reaction pressure, MPa | 3.0 | 1.0 | 4.0 | 3.0 | 2.5 | 3.0 |
| Hydrogen hydrocarbon molecule ratio | 3.0 | 6.0 | 5.0 | 4.0 | 5.0 | 1.5 |
| The heavy arene transformation efficiency, % (weight) | 58.21 | 49.88 | 71.66 | 51.30 | 60.23 | 64.89 |
| The BTX selectivity, % (weight) | 72.18 | 77.84 | 57.37 | 69.92 | 68.39 | 53.88 |
| The ring loss, % (weight) | 1.23 | 0.76 | 1.46 | 1.77 | 2.04 | 2.36 |
Claims (1)
1. a method that is used for carbon nine and above heavy aromatic hydrocarbon light and transalkylation is got Na
2O content is less than 0.10% (weight), SiO
2/ Al
2O
3Nano-ZSM-5 molecular sieve 60 grams and the Na of mol ratio 32, particle diameter 10～40nm
2O content mixes less than 0.15% kaolin 45 grams and 1 gram extrusion aid sesbania powder; With CP ammonium tetramolybdate [(NH
4)
2Mo
4O
13] 1.82 grams, 1.5 milliliters in CP nitric acid, 60 milliliters of wiring solution-formings of deionized water; Add this solution nano-ZSM-5 molecular sieve and kaolinic mixture thorough mixing, mediate evenly; Carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, and made catalyzer L; With the catalyzer L that makes, carry out heavy aromatic hydrocarbon light and the investigation of transalkylation reaction performance at fixed-bed reactor, be 2.5 hours at weight space velocity
-1, 380 ℃ of temperature of reaction, reaction pressure 3.0MPa, hydrogen and raw molecule are than under 4.0 conditions, and the heavy arene transformation efficiency is 54.66 weight %, and the BTX selectivity is 76.38 weight %, and the ring loss is 1.36 weight %.
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| KR101743293B1 (en) * | 2010-10-22 | 2017-06-05 | 에스케이이노베이션 주식회사 | Hydrocracking catalyst for preparing valuable light aromatic hydrocarbons from polycyclic aromatic hydrocarbons |
| CN102746091B (en) * | 2011-04-20 | 2015-04-08 | 中国石油化工股份有限公司 | Method for producing BTX (benzene, toluene and xylol) aromatic hydrocarbons and trimethylbenzene from heavy aromatic hydrocarbons |
| CN102746093B (en) * | 2011-04-20 | 2016-01-13 | 中国石油化工股份有限公司 | Heavy aromatics hydrocracking is utilized to increase production the method for BTX aromatic hydrocarbons and trimethylbenzene |
| CN102746092B (en) * | 2011-04-20 | 2015-04-08 | 中国石油化工股份有限公司 | Method for separating and producing 1,3,5-trimethylbenzene through hydrocracking heavy aromatic hydrocarbons |
| CN102909068B (en) * | 2011-08-01 | 2014-08-20 | 中国石油化工股份有限公司 | Catalyst of toluene disproportionation and alkyl transference, and preparation method and application thereof |
| CN104419455A (en) * | 2013-09-02 | 2015-03-18 | 中国科学院大连化学物理研究所 | Method for lightly producing high-octane gasoline blending component from heavy gasoline |
| CN104383961A (en) * | 2014-11-11 | 2015-03-04 | 中国海洋石油总公司 | Catalyst for hydrocracking heavy aromatics for producing high-purity BTX aromatics and preparing method of catalyst |
| CN107541260A (en) * | 2016-06-24 | 2018-01-05 | 深圳市新路田科技有限公司 | A kind of method and system for realizing heavy hydrocarbon lighting |
| KR102456344B1 (en) * | 2016-12-08 | 2022-10-21 | 쉘 인터내셔날 리써취 마트샤피지 비.브이. | Method of Preparation of Molybdenum-Platinum-Based Catalyst for Synthesis of Benzene by Transalkylation |
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| CN100998950A (en) * | 2006-01-11 | 2007-07-18 | 中国石油化工股份有限公司 | Catalyst used for heavy arene lightenation and alkyl transfer and its preparation method |
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| CN100998950A (en) * | 2006-01-11 | 2007-07-18 | 中国石油化工股份有限公司 | Catalyst used for heavy arene lightenation and alkyl transfer and its preparation method |
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