CN101811063B - Catalyst for alkyl transfer and conversion of C9 and C9+ heavy aromatics to light aromatics - Google Patents
Catalyst for alkyl transfer and conversion of C9 and C9+ heavy aromatics to light aromatics Download PDFInfo
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- CN101811063B CN101811063B CN200910056898A CN200910056898A CN101811063B CN 101811063 B CN101811063 B CN 101811063B CN 200910056898 A CN200910056898 A CN 200910056898A CN 200910056898 A CN200910056898 A CN 200910056898A CN 101811063 B CN101811063 B CN 101811063B
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Abstract
The invention relates to a catalyst for the alkyl transfer and the conversion of C9 and C9+ heavy aromatics to light aromatics, which mainly solves the existing technical problems of low heavy aromatic conversion rate, low target product selectivity, serious aromatic ring opening phenomena and catalyst requirement for noble metal loading in the process of processing C9 and C9+ heavy aromatics to increase the yield of benzene, methyl benzene and dimethyl benzene in the prior art. By adopting the technical scheme of comprising 20-90 parts of hydrogen nano zeolite and 10-80 parts of adhesive in parts by weight, wherein the mol ratio of SiO2 to Al2O3 in the hydrogen nano zeolite is 8-200, the invention well solves the problems, and can be used in industrial production for the conversion of heavy aromatics to light aromatics and the alkyl transfer.
Description
Technical field
The present invention relates to a kind of carbon nine and above heavy aromatic hydrocarbon light and transalkylation catalyst; Particularly about being raw material with carbon nine and above heavy arene thereof; Through lighting and transalkylation process raising the output benzene,toluene,xylene, do not need the catalyst of carried noble metal.
Background technology
Nano particle has tangible bulk effect, skin effect and quantum size effect; Nano zeolite is owing to have bigger external surface area and a higher intracrystalline diffusion rate, in the utilization rate that improves catalyst, strengthen big molecule 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 oil and coal process, is mainly derived from the byproduct that light oil cracking is produced ethylene unit; The extracting aromatic hydrocarbons of oil plant catalytic reforming; The long distillate catalytic reforming unit by-product C of polyester raw material factory
10(carbon ten) heavy aromatics; The byproduct of toluene disproportionation and transalkylation unit; Ethylene unit by-product ethylene bottom oil.Along with the increase of refining capacity, the construction in the large-scale ethylene production of megaton 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 existing ripe method of the processing and utilization of A (C9 aromatic) generally as the raw material of toluene disproportionation and transalkylation reaction, is used for making benzene and xylenes.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), methyl naphthalene (241.1～244.4 ℃ of boiling points, 30.5～34.9 ℃ of fusing points) etc., a part is as producing serial solvent naphtha; 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 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 xylenes 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 xylenes 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 xylenes, 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 technical 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 conversion ratio is on the low side, about 80% C
10Heavy aromatics is discharged at the bottom of the heavy aromatics Tata.
Second kind of technical 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 high selectivity paraxylene 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 molecular sieve catalyst.
Metal oxide catalyst mainly is chromium oxide (Cr
2O
3) and molybdenum oxide (MoO
3) catalyst, adopting this type catalyst 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) catalyst 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 conditions, during product is formed by weight percentage for containing benzene 9.74%, toluene 30.27%, xylenes 32.33% and non-aromatic hydrocarbons 0.16%.
Adopting the molecular sieve catalyst desired reaction temperature is low than metal oxide catalyst, helps avoiding catalysqt deactivation.
In USP4172813,3%WO by weight percentage
3, 5%MoO
3-60% modenite-40%Al
2O
3Be catalyst, make heavy reformate generation hydro-dealkylation and transalkylation reaction.Its reaction temperature 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 catalyst with the restricted index 1～12 of carried noble metal, high silica alumina ratio, low acid zeolite, make heavy reformate generation hydro-dealkylation and transalkylation reaction.Its reaction temperature is 427～540 ℃.
In USP 5001296, be catalyst with the MCM-22 zeolite of carried noble metal, can be at 315～482 ℃ with C
9The feedstock conversion of A content 96.8% (mole) is benzene, toluene and xylenes (BTX).
In CN 1117404, be catalyst 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 conversion ratio 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 catalyst respectively, at 350～450 ℃ with C
9The feedstock conversion of A content 97.95% (weight) is BTX, C
9The A conversion ratio is in 32.3～41.91% (weight).
In CN 1472182, the ZSM-5/ β zeolite composite molecular screen with carried noble metal is a catalyst respectively, at 350～450 ℃ with C
9The feedstock conversion of A content 97.95% (weight) is BTX, C
9The A conversion ratio is in 32.3～46% (weight).
In CN 101045208, be catalyst with β zeolite, modenite, ZSM-5 or the ZSM-12 that carries palladium, at 375 ℃ with C
9 +A, toluene reach or benzene is recycle feed, and conversion ratio 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 disposal ability of C10 is low; X/B is merely 1.7～2.0 in the product, and purpose product xylenes yield is low, is unfavorable for increasing economic efficiency.
In CN 1752058, be catalyst with the metal of load bismuth and molybdenum or the large pore zeolite of oxide, can handle the raw material that contains certain carbon 11 above aromatic hydrocarbons, but the C10 aromartic conversion ratio is lower.
Need carried noble metal in the above-mentioned document mostly; Increased the catalyst cost; All contain a large amount of toluene in the raw material that uses simultaneously; Heavy aromatics, the particularly disposal ability of the above heavy aromatics of C10 are weak, the heavy arene conversion ratio is low, the purpose product yield is low, the aromatic ring open loop is serious, catalyst 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; The technical problem that the heavy arene conversion ratio is low when preparing benzene,toluene,xylene through lighting and transalkylation process, the purpose product selectivity is low, the aromatic ring open loop serious, catalyst needs carried noble metal provides a kind of new carbon nine and above heavy aromatic hydrocarbon light and transalkylation catalyst.This catalyst is used for carbon nine and above heavy aromatic hydrocarbon light and transalkylation reaction; Have that 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 xylenes products, and this catalyst have the catalytic activity height; The heavy arene treating 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 carbon nine and above heavy aromatic hydrocarbon light and transalkylation catalyst comprise 20～90 parts of SiO in parts by weight
2/ Al
2O
3Mol ratio is 8～200 Hydrogen nano zeolite and 10～80 parts binding agent.
In the technique scheme, the Hydrogen nano zeolite is selected from least a among β zeolite, modenite, the ZSM-5.Binding agent is selected from aluminium oxide, boehmite, silica, oxidation sial, bentonite, kaolin, diatomite or the montmorillonite at least a, and preferred version is selected from least a in aluminium oxide, boehmite, silica, the kaolin.Hydrogen nano zeolite priority scheme is selected from β zeolite, modenite or its mixture, and the particle diameter of nano zeolite is 5～100nm, and preferable range is 20～100nm.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.The catalyst preferred version is also to comprise group vib metal or its oxide in the catalyst, and the weight ratio preferable range of its consumption and Hydrogen nano zeolite is 0.001～0.5: 1, and more preferably scope is 0.005～0.3: 1.
In the technique scheme, molybdenum or its oxide are that roasting obtains later on through fully contacting also under certain condition with modifier that contains molybdenum compound and Hydrogen nano zeolite, thereby realize the Hydrogen nano zeolite is carried out modification.The modifier that contains molybdenum compound is selected from least a in molybdenum chloride, molybdenum bisuphide, sodium molybdate, potassium molybdate, ammonium dimolybdate, ammonium tetramolybdate, the ammonium heptamolybdate.
In the technique scheme, chromium or its oxide are that roasting obtains later on through fully contacting also under certain condition with modifier that contains chromium compound and Hydrogen nano zeolite, thereby realize the Hydrogen nano zeolite is carried out modification.The modifier that contains chromium compound is selected from least a in chromium chloride, sodium dichromate, chromic nitrate, the chromium trioxide.
In the technique scheme, tungsten or its oxide are that roasting obtains later on through fully contacting also under certain condition with modifier that contains tungsten compound and Hydrogen nano zeolite, thereby realize the Hydrogen nano zeolite is carried out modification.The modifier that contains tungsten compound is selected from least a in wolframic acid, sodium tungstate, potassium tungstate, artificial schellite, ammonium metatungstate, ammonium paratungstate, the phosphotungstic acid.
Catalyst provided by the invention is a kind of carbon nine and above heavy aromatic hydrocarbon light and transalkylation catalyst, can be used for preparing benzene, toluene and xylenes.
Among the present invention owing to adopt nano zeolite, catalyst acid position utilization rate high, acid strength 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 catalyst provided by the invention; Being used for pure heavy arene is that raw material carries out lighting and transalkylation reaction, and 300～550 ℃ of temperature, reaction pressure is under the 3.0MPa condition; Conversion ratio can reach 62.83%; Selectivity can reach 79.60%, and the aromatic ring loss is reduced to 0.95%, has obtained better technical effect.
The present invention uses fixed bed reactors to carry out reactivity worth and investigates 14 millimeters of reactor inside diameter φ, 500 millimeters of length, stainless steel.Adopt electrical heating, temperature is controlled automatically.5 millimeters beades of reactor bottom filling φ are as supporter, filling catalyst 5 grams in the reactor, and 5 millimeters beades 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, xylenes, 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 industry Aromatic Hydrocarbon United Plant, test 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.
The specific 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%, boehmite 45 grams and the 1 gram extrusion aid sesbania powder of calcination loss 30% mix; Add 1.5 milliliters in chemical pure nitric acid, 60 milliliters of deionized waters; Fully mix, mediate 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%, boehmite 45 grams and the 1 gram extrusion aid sesbania powder of calcination loss 30% mix; Add 1.5 milliliters in chemical pure nitric acid, 60 milliliters of deionized waters; Fully mix, mediate 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%, boehmite 45 grams and the 1 gram extrusion aid sesbania powder of calcination loss 30% mix; Add 1.5 milliliters in chemical pure nitric acid, 60 milliliters of deionized waters; Fully mix, mediate evenly; Carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, and made catalyst 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 chemical pure nitric acid, 60 milliliters of deionized waters, fully mix, mediate evenly, carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, make catalyst 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 chemical pure nitric acid, 60 milliliters of deionized waters, fully mix, mediate evenly, carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, make catalyst 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 chemical pure nitric acid, 60 milliliters of deionized waters; Fully mix, mediate evenly, carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, make catalyst 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% silica 40 grams and 1 gram extrusion aid sesbania powder; Add 1.5 milliliters in chemical pure nitric acid, 60 milliliters of deionized waters; Fully mix, mediate evenly, carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, make catalyst 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%, boehmite 50 grams and the 1 gram extrusion aid sesbania powder of calcination loss 30% mix; Add 2 milliliters in chemical pure nitric acid, 60 milliliters of deionized waters; Fully mix, mediate evenly; Carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, and made catalyst 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%, boehmite 50 grams and the 1 gram extrusion aid sesbania powder of calcination loss 30% mix; Add 2 milliliters in chemical pure nitric acid, 60 milliliters of deionized waters; Fully mix, mediate 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%, boehmite 45 grams and the 1 gram extrusion aid sesbania powder of calcination loss 30% mix; Add 1.5 milliliters in chemical pure nitric acid, 60 milliliters of deionized waters; Fully mix, mediate evenly; Carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, and made catalyst X1.
[comparative example 2]
Get Na
2O content is less than 0.10% (weight), SiO
2/ Al
2O
3Conventional modenite 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 chemical pure nitric acid, 60 milliliters of deionized waters, fully mix, mediate evenly, carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, make catalyst 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 reactors, and weight space velocity is 2.5 hours
-1, 440 ℃ of reaction temperatures, 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 | Xylenes | 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 catalyst numbering | A | B | C | D | E | F | G | H | I |
| The heavy arene conversion ratio, % (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]
Catalyst X1, X2 with comparative example 1～2 makes carry out heavy aromatic hydrocarbon light and the investigation of transalkylation reaction performance at fixed bed reactors, and weight space velocity is 2.5 hours
-1, 440 ℃ of reaction temperatures, 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 catalyst numbering | X1 | X2 |
| The heavy arene conversion ratio, % (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%, boehmite 45 grams and the 1 gram extrusion aid sesbania powder of calcination loss 30% mix; With chemical pure ammonium heptamolybdate [(NH
4)
6Mo
7O
24] 4.6 grams, 2 milliliters in chemical pure nitric acid, 60 milliliters of wiring solution-formings of deionized water; The mixture that adds this solution nanometer β zeolite and boehmite fully mixes, mediates evenly; Carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, and made catalyst 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 chemical pure ammonium heptamolybdate [(NH
4)
6Mo
7O
24] 0.46 gram, 2 milliliters in chemical pure nitric acid, 60 milliliters of wiring solution-formings of deionized water, add nano mordenite zeolite and γ-Al to this solution
2O
3Mixture fully mix, mediate evenly, carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, make catalyst 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 chemical pure ammonium tetramolybdate [(NH
4)
2Mo
4O
13] 1.82 grams, 1.5 milliliters in chemical pure nitric acid, 60 milliliters of wiring solution-formings of deionized water; Fully mix this solution adding nano-ZSM-5 molecular sieve and kaolinic mixture, mediate evenly; Carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, and made catalyst 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%, boehmite 50 grams and the 1 gram extrusion aid sesbania powder of calcination loss 30% mix; With chemical pure ammonium heptamolybdate [(NH
4)
6Mo
7O
24] 4.6 grams, 2 milliliters in chemical pure nitric acid, 60 milliliters of wiring solution-formings of deionized water; The mixture that adds this solution nanometer β zeolite, nano mordenite and boehmite fully mixes, mediates evenly; Carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, and made catalyst 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%, boehmite 45 grams and the 1 gram extrusion aid sesbania powder of calcination loss 30% mix; With chemical pure ammonium paratungstate [H
40N
10W
12O
41] 16.4 grams, 2 milliliters in chemical pure nitric acid, 60 milliliters of wiring solution-formings of deionized water; The mixture that adds this solution nanometer β zeolite and boehmite fully mixes, mediates evenly; 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%, boehmite 45 grams and the 1 gram extrusion aid sesbania powder of calcination loss 30% mix; With chemical pure chromic nitrate [Cr (NO
3) 9H
2O] 7.7 grams, 2 milliliters in chemical pure nitric acid, 60 milliliters of wiring solution-formings of deionized water; The mixture that adds this solution nanometer β zeolite and boehmite fully mixes, mediates evenly; Carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, and made catalyst O.
[embodiment 25～30]
Catalyst J～O with embodiment 19～24 makes carries out heavy aromatic hydrocarbon light and the investigation of transalkylation reaction performance at fixed bed reactors, and weight space velocity is 2.5 hours
-1, 380 ℃ of reaction temperatures, 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 catalyst numbering | J | K | L | M | N | O |
| The heavy arene conversion ratio, % (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%, boehmite 45 grams and the 1 gram extrusion aid sesbania powder of calcination loss 30% mix; Add 1.5 milliliters in chemical pure nitric acid, 60 milliliters of deionized waters; Fully mix, 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 catalyst X3, wherein contains palladium 0.36%.
[comparative example 6]
Get Na
2O content is less than 0.10% (weight), SiO
2/ Al
2O
3Conventional modenite 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 chemical pure nitric acid, 60 milliliters of deionized waters; Fully mix, 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 catalyst X4, wherein contains palladium 0.25%.
[comparative example 7～8]
Catalyst X3, X4 with comparative example 5～6 makes carry out heavy aromatic hydrocarbon light and the investigation of transalkylation reaction performance at fixed bed reactors, and weight space velocity is 2.5 hours
-1, 400 ℃ of reaction temperatures, 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 catalyst numbering | X3 | X4 |
| The heavy arene conversion ratio, % (weight) | 39.60 | 42.84 |
| The BTX selectivity, % (weight) | 66.78 | 67.35 |
| The ring loss, % (weight) | 5.40 | 5.94 |
Claims (1)
1. a carbon nine and above heavy aromatic hydrocarbon light and transalkylation catalyst are got Na
2The O weight content less than 0.10%, 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%, boehmite 45 grams and the 1 gram extrusion aid sesbania powder of calcination loss 30% mix; Add 1.5 milliliters in chemical pure nitric acid, 60 milliliters of deionized waters; Fully mix, mediate evenly; Carry out extruded moulding, 150 ℃ of oven dry pelletizings after 4 hours, 600 ℃ of roastings 4 hours, and made catalyst A;
With the catalyst A that makes, carry out heavy aromatic hydrocarbon light and the investigation of transalkylation reaction performance at fixed bed reactors, weight space velocity is 2.5 hours
-1, 440 ℃ of reaction temperatures, reaction pressure 3.0MPa, hydrogen and raw molecule are than 4.0; Raw material weight percentage consists of: non-virtue is 0.04%, and benzene is 0.02%, toluene 0.00%, ethylbenzene 0.17%, xylenes 0.03%, indane 1.54%, C
9Aromatic hydrocarbons is 78.04%, C
10 +Aromatic hydrocarbons is 20.16%;
Evaluation result is: the heavy arene conversion ratio is 47.46 weight %, and the BTX selectivity is 79.60 weight %, and the ring loss is 0.95 weight %.
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| 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 |
| CN108786902B (en) * | 2017-05-02 | 2021-03-05 | 中国石油化工股份有限公司 | Heavy aromatic hydrocarbon conversion catalyst and preparation method thereof |
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| EP3539651A1 (en) | 2018-03-14 | 2019-09-18 | Saudi Arabian Oil Company | Method of heavy reformate conversion into btx over metal-impregnated zsm-5+layered mordenite zeolite composite catalyst; said composite catalyst |
| EP3539650B1 (en) | 2018-03-14 | 2021-03-31 | Saudi Arabian Oil Company | Methods of producing composite zeolite catalysts for heavy reformate conversion into xylenes |
| EP3539649B1 (en) | 2018-03-14 | 2020-11-18 | Saudi Arabian Oil Company | Methods of producing composite zeolite catalysts for heavy reformate conversion into xylenes |
| EP3539652A1 (en) | 2018-03-14 | 2019-09-18 | Saudi Arabian Oil Company | Method of heavy reformate conversion into btx over metal-impregnated zsm-5+mesoporous mordenite zeolite composite catalyst |
| CN109622002B (en) * | 2018-12-17 | 2021-12-21 | 西北大学 | Preparation method of catalyst for improving BTX yield |
| US11261098B2 (en) | 2019-11-06 | 2022-03-01 | Saudi Arabian Oil Company | Systems and methods for preparing nano-sized crystals of BEA zeolite with metal oxide for hydrocarbon conversions |
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| EP3539654A1 (en) * | 2018-03-14 | 2019-09-18 | Saudi Arabian Oil Company | Method of heavy reformate conversion into btx over metal-impregnated zsm-5+nanocrystalline beta zeolite composite catalyst; said composite catalyst |
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