CN103121896B - Method for converting polycyclic aromatic hydrocarbons into monocyclic aromatic hydrocarbons - Google Patents
Method for converting polycyclic aromatic hydrocarbons into monocyclic aromatic hydrocarbons Download PDFInfo
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Abstract
The invention relates to a method for converting polycyclic aromatic hydrocarbons into monocyclic aromatic hydrocarbons, mainly solving the problems in the prior art that the conversion level of polycyclic aromatic hydrocarbons is low, the monocyclic aromatic hydrocarbon yield and selectivity are low and the catalyst deactivation rate is high. The problems are better solved by adopting the technical scheme that polycyclic aromatic hydrocarbon mixtures and hydrogen are taken as the raw materials and are contacted with a catalyst in a fixed bend reactor to react under the conditions that the reaction temperature is 335-440 DEG C, the pressure is 4-7MPa, the weight hourly space velocity is 1-3hr<-1> and the hydrogen/hydrocarbon mole ratio is 4.0-8.0 to generate monocyclic aromatic hydrocarbon mixtures. The method can be used in the industrial production of converting heavy polycyclic aromatic hydrocarbons into monocyclic aromatic hydrocarbons.
Description
Technical field
The present invention relates to a kind of method that polycyclic aromatic hydrocarbons is converted into mononuclear aromatics.
Background technology
In recent years, along with the continuous intensification of oil product degree of heaviness in world petroleum resource, how under the prerequisite meeting high standard environmental requirement, effectively utilize these heavy oil resources and meet and improve daily life needs and become an important research topic.In heavy oil product, the annual production of heavy aromatics increases year by year, and except seldom a part is used as except organic solvent, major part is mixed in fuel and used, and no matter from environmental protection or economic angle, Heavy Aromatic Hydrocarbons is not all fully utilized effectively.The source of heavy aromatics is mainly present in the cracking process of catalytic reforming and hydrocarbon, and the content as the condensed ring naphthalene series aromatics of heavy in catalytic cracking light cycle oil (LCO) can reach 70%.These heavy aromaticss are utilized to develop the industrial foundation organic raw material of high added value, as a good selection beyond doubt such as benzene,toluene,xylene (BTX).At present, domestic triphen is produced and is mainly utilized straight-run spirit, petroleum naphtha to obtain through noble metal platinum reforming process and preparing ethylene by steam cracking technique, and because of starving, the output of benzene and its derivative is restricted to a great extent.China's light and textile industries' development is in recent years very fast, the annual downstream derivative produce product needing a large amount of import benzene, and import volume increases very fast, seeks aromatic hydrocarbons yield-increasing technology very urgent.
Nippon Oil(Nippon Mitsubishi Oil) report on January 21st, 2010, will develop the technical matters of producing aromatic hydrocarbon product with solar oil (LCO).Compared with consuming the traditional technology of hydrogen in a large number, this new technology can cut down production cost, is expected to realization and commercially produces.
USP4,341,622 disclose a kind of method utilizing heavy reformate to produce BTX.The method employing restricted index is 1 ~ 12, silica/alumina molar ratio (silica alumina ratio) is more than 12, the zeolite of low acid activity is catalyzer, reformate is reacted under the condition of 427 ~ 540 DEG C, then resultant fractionation by distillation is obtained benzene, toluene and dimethylbenzene.Described catalyzer contains the VIII precious metal of hydro-dealkylation function, preferred platinum, and the silica alumina ratio of zeolite used is preferably greater than 200, and more preferably greater than 500, preferred zeolite is ZSM-5.Selecting the zeolite of high silica alumina ratio for reducing zeolite acidity, retaining dimethylbenzene as far as possible and not being converted in the reaction.
US2007062848A1 discloses and a kind ofly first will carry out selective opening and de-alkyl after polycyclic aromatic hydrocarbons fractional saturation again to obtain the method for light aromatics.The method can to meet in feed stream polycyclic aromatic hydrocarbon content at more than 20wt%, saturation stage temperature at 300 ~ 500 DEG C, pressure 2 ~ 10MPa; Open loop phase temperature at 200 ~ 600 DEG C, pressure 1 ~ 12MPa.Because two-stage catalytic agent is contained in same reactor, so require that logistics needs to ensure that certain residence time could obtain good transformation efficiency, therefore air speed is lower.
CN1117404A discloses a kind of from containing C
9 +the hydrocarbon feed of aromatic hydrocarbons produces the catalyzer of benzene, toluene and dimethylbenzene, and this catalyzer is the γ-or the η-Al that weigh % in the ZSM-5 zeolite of 30 ~ 70 % by weight (with carriers for benchmark) and 30 ~ 70
2o
3for carrier, the palladium composition of the rhenium of the heavy % of load 0.1 ~ 0.5, the tin of 0.1 ~ 0.5 heavy %, 0.05 ~ 0.3 heavy % platinum or 0.2 ~ 0.8 heavy %.350 ~ 450 DEG C, 0.5 ~ 3.5MPa, weight space velocity 1 ~ 5 time
-1, hydrogen/hydrocarbon (volume ratio) 500 ~ 1200 operational condition under, this catalyzer has higher catalytic activity and stability, and lower hydrogen consumption.
CN1472181A discloses a kind of heavy aromatics lightening catalyst, comprise group VIII metal and the complex carrier of 0.01 ~ 2.0 heavy %, described complex carrier comprises the aluminum oxide of the ZSM-5 zeolite of 30 ~ 70 heavy %, mordenite and 10 ~ 65 % by weight of 5 ~ 20 heavy %.This catalyzer is used for heavy aromatic hydrocarbon light, can improve C
9 +the productive rate of aromatics conversion rate and benzene and dimethylbenzene, and reduce carbon distribution.
Summary of the invention
Technical problem to be solved by this invention is low in order to overcome polycyclic aromatic hydrocarbons depth of conversion when the heavy polycyclic aromatic hydrocarbons existed in prior art is converted into mononuclear aromatics reaction, mononuclear aromatics yield is low and selectivity is low, the problem that catalyst deactivation rate is fast, provides a kind of new polycyclic aromatic hydrocarbons to be converted into the method for mononuclear aromatics.It is high that the method has polycyclic aromatic hydrocarbons depth of conversion, and mononuclear aromatics yield is high and selectivity is high, the advantage that catalyst deactivation rate is slow.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of polycyclic aromatic hydrocarbons is converted into list
The method of Polycyclic aromatic hydrocarbons, with Polycyclic Aromatic Hydrocarbon Mixture and hydrogen for raw material is by fixed-bed reactor, at temperature of reaction 335 ~ 440 DEG C, reaction pressure 4 ~ 7MPa, weight hourly space velocity degree 1 ~ 3hr
-1, hydrogen hydrocarbon mol ratio 4.0 ~ 8.0 condition under to react with catalyst exposure and generate mononuclear aromatics mixture, catalyst wherein used comprises following component:
A) 34.5 ~ 60%FAU type zeolite and the mixture being selected from least one molecular sieve in MOR, BEA, MFI or MCM-22;
B) 39.5 ~ 65% at least one be selected from gama-alumina, η-aluminum oxide or pseudo-boehmite are binding agent;
C) 0.05 ~ 0.9% at least one metal in Pt, Pd or Ir or its oxide compound is selected from.
In technique scheme, Polycyclic Aromatic Hydrocarbon Mixture is mainly naphthalene series compound; Mononuclear aromatics mixture comprises benzene, toluene, ethylbenzene, dimethylbenzene, C9 aromatic and C10 aromartic.
In technique scheme, in used catalyst composition FAU type zeolite and at least one molecular sieve be selected from MOR, BEA, MFI or MCM-22 be sodium weight content lower than 2% Hydrogen or ammonium type zeolite; In mixture, the amount preferable range of FAU type zeolite is 50 ~ 90% by weight percentage, and the amount preferable range being selected from least one molecular sieve in MOR, BEA, MFI or MCM-22 is 10 ~ 50%.
The preparation method of used catalyst in the inventive method, comprises the following steps:
1., after the FAU type zeolite of aequum and the binding agent that is selected from the mixture of at least one molecular sieve in MOR, BEA, MFI or MCM-22 and at least one be selected from gama-alumina, η-aluminum oxide, pseudo-boehmite of aequum being carried out kneading, shaping, drying, support of the catalyst is obtained at 450 ~ 650 DEG C of roasting 0.5 ~ 24h;
2. the precursor solution being selected from least one metal in Pt, Pd or Ir or its oxide compound of aequum is impregnated into 0.5 ~ 24h in support of the catalyst in 30 ~ 50 DEG C, obtains finished catalyst at 300 ~ 450 DEG C of roasting 0.5 ~ 24h after drying.
In technique scheme, in catalyst support preparation process, preferred version can add the extrusion aid calculating 2 ~ 5% weight by carrier butt, such as sesbania powder; Can add that to calculate by carrier butt the acid solution that 3 ~ 6% weight are selected from least one in hydrochloric acid, nitric acid, acetic acid, tartrate, citric acid or oxalic acid and water volume ratio 1: 1 ~ 1: 5 be gelatinizing agent.
The precursor solution preferred version of Pt metal used in technique scheme is Platinic chloride; The precursor solution preferred version of metal Pd is at least one in Palladous nitrate or Palladous chloride; The precursor solution preferred version of metal Ir is chloro-iridic acid.
Method provided by the invention is a kind of method being converted into mononuclear aromatics for heavy polycyclic aromatic hydrocarbons, and the method can be used for producing benzene, toluene and dimethylbenzene.
Owing to have selected the type zeolite such as FAU, BEA of three-dimensional macropore as catalyst acid center in the present invention, be conducive to the acid site that heavy arene macromole enters in duct and carry out ring-opening reaction, product molecule after conversion can passing hole channel rapid diffusion, thus has delayed the deactivation rate of catalyzer; Be there is by load the precious metal element of hydrogenating function, control its charge capacity at a zone of reasonableness, effectively can improve the degree of unsaturation of Polycyclic Aromatic Hydrocarbon Mixture raw material, help deep conversion polycyclic aromatic hydrocarbons; The rational proportion of catalyst acid center and metallic element occurs with the de-alkyl of part, transalkylation and light aromatic hydrocarbons aromatization during will make hydrogenation open loop simultaneously, these reactions will retain original mononuclear aromatics component in feedstream as far as possible, maximize with the yield and selectivity that make mononuclear aromatics, achieve good technique effect.
The present invention use overcritical fixed-bed reactor carry out polycyclic aromatic hydrocarbons be converted into mononuclear aromatics reactivity worth investigate, reactor inside diameter Ф 12 millimeters, length 800 millimeters, stainless steel.Adopt electrically heated, temperature automatic control.It is upholder that reactor bottom fills Ф 2 ~ 3 millimeters of granulated glass spherees, catalyst filling 5 grams in reactor, and Ф 2 ~ 3 millimeters of granulated glass spherees are filled on top, is made for the use of raw material preheating and vaporization.Raw material Polycyclic Aromatic Hydrocarbon Mixture mixes with hydrogen, passes through beds, makes polycyclic aromatic hydrocarbons be converted into the mononuclear aromatics such as benzene,toluene,xylene.
Polycyclic Aromatic Hydrocarbon Mixture is autogamy raw material, and experimental data is calculated as follows.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
Be 30g FAU type zeolite (being purchased Hydrogen), 10g BEA type zeolite (being purchased Hydrogen) and 60g γ-Al by butt
2o
3(industrial goods) add mixing tank to evenly, in mixture, then add 3g sesbania powder, 5g volume ratio 1: 1 HNO
3solution and 40g deionized water, the dough being suitable for extruding evenly is made in grinding.It extruded by mould, shape is elongated cylindrical (diameter 1.7mm), in 550 DEG C of roasting 4h after 120 DEG C of oven dry, is then cut into the carrier granule (1.7 × 4.0mm) of consistent size, is designated as Z1.
Flooded carrier granule at 40 DEG C by Platinic chloride wiring solution-forming, the amount containing Pt in steeping fluid is 0.1% of carrier butt weight, and dipping 8h also after drying, at 450 DEG C of roasting 3h, obtains finished catalyst A.
[embodiment 2 ~ 6]
The preparation method provided according to embodiment 1 and process, in the process of flooding Z1 carrier granule, prepared a series of finished catalyst, in table 1 by the kind changing metal precursor in steeping fluid.
Table 1
| Catalyzer is numbered | Carrier forms | Metal precursor | Metal impregnation amount |
| B | Z1 | Palladous nitrate | 0.1wt％Pd |
| C | Z1 | Chloro-iridic acid | 0.1wt％Ir |
| D | Z1 | Platinic chloride, Palladous nitrate | 0.032wt％Pt、0.068wt％Pd |
| E | Z1 | Platinic chloride, chloro-iridic acid | 0.05wt％Pt、0.05wt％Ir |
| F | Z1 | Palladous nitrate, chloro-iridic acid | 0.032wt％Ir、0.068wt％Pd |
[embodiment 7 ~ 12]
The preparation method provided according to embodiment 1 and process, in the process of flooding Z1 carrier granule, prepared a series of finished catalyst, in table 2 by the pickup changing metal.
Table 2
| Catalyzer is numbered | Carrier forms | Metal precursor | Metal impregnation amount |
| G | Z1 | Platinic chloride | 0.2wt％Pt |
| H | Z1 | Chloro-iridic acid | 0.2wt％Ir |
| I | Z1 | Palladous nitrate | 0.2wt％Pd |
| J | Z1 | Platinic chloride, Palladous nitrate | 0.09wt％Pt、0.06wt％Pd |
| K | Z1 | Palladous nitrate, chloro-iridic acid | 0.09wt％Ir、0.06wt％Pd |
| L | Z1 | Platinic chloride, chloro-iridic acid | 0.07wt％Pt、0.07wt％Ir |
[embodiment 13 ~ 20]
The preparation method provided according to embodiment 1 and process, by changing the contamination of metal precursor in carrier composition and steeping fluid, prepared a series of finished catalyst, in table 3.
Table 3
(wherein B is benzene with catalyst A ~ T (highest response pressure 10MPa, use temperature are room temperature ~ 600 DEG C) investigation on overcritical fixed-bed reactor that embodiment 1 ~ 20 is obtained, Polycyclic Aromatic Hydrocarbon Mixture to be converted into BTX, T is toluene, and X is dimethylbenzene) etc. the ability of mononuclear aromatics.Table 4 is Polycyclic Aromatic Hydrocarbon Mixture raw material composition.Catalyst loading 5g, at temperature of reaction 370 DEG C, reaction pressure 6MPa, weight hourly space velocity degree 2.0hr
-1, contact with catalyzer under hydrogen/hydrocarbon mol ratio 5.0 condition, product to be reclaimed and component detects, conversion results is shown in Table 5.
Table 4 raw material forms
| Raw material forms | Non-aromatic | Benzene | Toluene | Ethylbenzene | Dimethylbenzene | Perhydronaphthalene | Naphthane | Naphthalene |
| Content (wt%) | 0.02 | 24.54 | 24.61 | 5 | 0.02 | 14.81 | 15.25 | 15.75 |
Table 5 polycyclic aromatic hydrocarbons conversion results
| Catalyzer is numbered | Total conversion rate (wt%) | Mononuclear aromatics selectivity (wt%) | BTX selectivity (wt%) |
| A | 70.5 | 61.2 | 39.6 |
| B | 73.1 | 65.3 | 43.8 |
| C | 68.2 | 63.5 | 38.9 |
| D | 71.8 | 64.0 | 42.2 |
| E | 69.4 | 61.6 | 40.8 |
| F | 71.0 | 64.2 | 43.0 |
| G | 78.3 | 66.1 | 44.2 |
| H | 76.5 | 65.6 | 43.9 |
| I | 80.3 | 65.9 | 45.0 |
| J | 79.4 | 66.3 | 44.8 |
| K | 77.3 | 65.2 | 43.5 |
| L | 76.1 | 64.8 | 42.4 |
| M | 71.0 | 60.3 | 37.2 |
| N | 67.4 | 59.8 | 38.3 |
| O | 65.5 | 58.1 | 33.4 |
| P | 72.3 | 64.9 | 43.0 |
| Q | 67.2 | 59.1 | 36.6 |
| R | 78.9 | 66.3 | 43.2 |
| S | 80.3 | 65.4 | 42.8 |
| T | 72.1 | 60.2 | 39.5 |
[embodiment 21 ~ 26]
Catalyst A ~ the F obtained by embodiment 1 ~ 6 investigates ability Polycyclic Aromatic Hydrocarbon Mixture being converted into the mononuclear aromatics such as BTX on overcritical fixed-bed reactor.Catalyst loading 5g, at temperature of reaction 400 DEG C, reaction pressure 6MPa, weight hourly space velocity degree 2.0hr
-1, contact with catalyzer under hydrogen/hydrocarbon mol ratio 5.0 condition, product to be reclaimed and component detects, conversion results is shown in Table 6.
Table 6 polycyclic aromatic hydrocarbons conversion results
| Catalyzer is numbered | Total conversion rate (wt%) | Mononuclear aromatics selectivity (wt%) | BTX selectivity (wt%) |
| A | 79.7 | 70.6 | 46.5 |
| B | 80.1 | 73.0 | 51.6 |
| C | 75.6 | 72.6 | 46.3 |
| D | 77.6 | 71.3 | 50.2 |
| E | 77.3 | 69.2 | 47.1 |
| F | 80.7 | 72.5 | 50.0 |
[embodiment 27 ~ 32]
Catalyst A ~ the F obtained by embodiment 1 ~ 6 investigates ability Polycyclic Aromatic Hydrocarbon Mixture being converted into the mononuclear aromatics such as BTX on overcritical fixed-bed reactor.Catalyst loading 5g, at temperature of reaction 370 DEG C, reaction pressure 5MPa, weight hourly space velocity degree 2.0hr
-1, contact with catalyzer under hydrogen/hydrocarbon mol ratio 5.0 condition, product to be reclaimed and component detects, conversion results is shown in Table 7.
Table 7 polycyclic aromatic hydrocarbons conversion results
| Catalyzer is numbered | Total conversion rate (wt%) | Mononuclear aromatics selectivity (wt%) | BTX selectivity (wt%) |
| A | 68.3 | 60.5 | 38.3 |
| B | 71.0 | 64.4 | 42.2 |
| C | 66.1 | 62.1 | 37.5 |
| D | 69.3 | 63.7 | 41.6 |
| E | 67.0 | 62.3 | 39.4 |
| F | 69.4 | 63.0 | 42.2 |
[embodiment 33 ~ 38]
Catalyst A ~ the F obtained by embodiment 1 ~ 6 investigates ability Polycyclic Aromatic Hydrocarbon Mixture being converted into the mononuclear aromatics such as BTX on overcritical fixed-bed reactor.Catalyst loading 5g, at temperature of reaction 370 DEG C, reaction pressure 6MPa, weight hourly space velocity degree 3.0hr
-1, contact with catalyzer under hydrogen/hydrocarbon mol ratio 5.0 condition, product to be reclaimed and component detects, conversion results is shown in Table 8.
Table 8 polycyclic aromatic hydrocarbons conversion results
| Catalyzer is numbered | Total conversion rate (wt%) | Mononuclear aromatics selectivity (wt%) | BTX selectivity (wt%) |
| A | 67.1 | 62.9 | 40.2 |
| B | 70.0 | 66.8 | 44.6 |
| C | 65.2 | 64.5 | 39.4 |
| D | 68.2 | 65.7 | 43.1 |
| E | 66.3 | 64.2 | 41.5 |
| F | 68.1 | 65.7 | 44.0 |
[embodiment 39 ~ 44]
Catalyst A ~ the F obtained by embodiment 1 ~ 6 investigates ability Polycyclic Aromatic Hydrocarbon Mixture being converted into the mononuclear aromatics such as BTX on overcritical fixed-bed reactor.Catalyst loading 5g, at temperature of reaction 370 DEG C, reaction pressure 6MPa, weight hourly space velocity degree 2.0hr
-1, contact with catalyzer under hydrogen/hydrocarbon mol ratio 7.0 condition, product to be reclaimed and component detects, conversion results is shown in Table 9.
Table 9 polycyclic aromatic hydrocarbons conversion results
| Catalyzer is numbered | Total conversion rate (wt%) | Mononuclear aromatics selectivity (wt%) | BTX selectivity (wt%) |
| A | 70.9 | 61.8 | 39.9 |
| B | 74.0 | 65.7 | 44.5 |
| C | 68.9 | 63.9 | 39.2 |
| D | 72.3 | 64.7 | 42.7 |
| E | 69.9 | 62.0 | 41.4 |
| F | 71.5 | 65.5 | 44.0 |
[comparative example 1 ~ 6]
Catalyst A ~ the F obtained by embodiment 1 ~ 6 investigates ability Polycyclic Aromatic Hydrocarbon Mixture being converted into the mononuclear aromatics such as BTX on overcritical fixed-bed reactor.Catalyst loading 5g, at temperature of reaction 370 DEG C, reaction pressure 5MPa, weight hourly space velocity degree 2.5hr
-1, contact with catalyzer under hydrogen/hydrocarbon mol ratio 6.0 condition, product to be reclaimed and component detects, conversion results is shown in Table 10.
Table 10 polycyclic aromatic hydrocarbons conversion results
| Catalyzer is numbered | Total conversion rate (wt%) | Mononuclear aromatics selectivity (wt%) | BTX selectivity (wt%) |
| A | 69.3 | 63.1 | 40.8 |
| B | 70.4 | 66.0 | 45.2 |
| C | 65.9 | 65.1 | 40.2 |
| D | 67.1 | 64.8 | 44.1 |
| E | 67.7 | 62.6 | 41.3 |
| F | 70.0 | 65.9 | 44.4 |
Claims (2)
1. polycyclic aromatic hydrocarbons is converted into a method for mononuclear aromatics, with Polycyclic Aromatic Hydrocarbon Mixture and hydrogen for raw material is by fixed-bed reactor, at temperature of reaction 335 ~ 440 DEG C, reaction pressure 4 ~ 7MPa, weight hourly space velocity degree 1 ~ 3hr
-1, hydrogen/hydrocarbon mol ratio 4.0 ~ 8.0 condition under to react with catalyst exposure and generate mononuclear aromatics mixture, catalyst wherein used comprises following component:
A) 34.5 ~ 60%FAU type zeolite and the mixture being selected from least one molecular sieve in MOR, BEA, MFI or MCM-22;
B) 39.5 ~ 65% at least one be selected from gama-alumina, η-aluminum oxide or pseudo-boehmite are binding agent;
C) 0.05 ~ 0.9% at least one metal in Pt, Pd or Ir or its oxide compound is selected from;
The preparation method of used catalyst, comprises the following steps:
1., after FAU type zeolite and the mixture that is selected from least one molecular sieve in MOR, BEA, MFI or MCM-22 and the binding agent of at least one be selected from gama-alumina, η-aluminum oxide, pseudo-boehmite being carried out kneading, shaping, drying, support of the catalyst is obtained at 450 ~ 650 DEG C of roasting 0.5 ~ 24h;
2. the precursor solution of at least one metal be selected from Pt, Pd or Ir or its oxide compound is impregnated into 0.5 ~ 24h in support of the catalyst in 30 ~ 50 DEG C, obtains finished catalyst at 300 ~ 450 DEG C of roasting 0.5 ~ 24h after drying;
Add in catalyst support preparation process and press the auxiliary agent that carrier butt calculates 2 ~ 5% weight; Add that to calculate by carrier butt the acid solution that 3 ~ 6% weight are selected from least one in hydrochloric acid, nitric acid, acetic acid, tartrate, citric acid or oxalic acid and water volume ratio 1:1 ~ 1:5 be gelatinizing agent; The precursor solution of Pt metal is Platinic chloride; The precursor solution of metal Pd is at least one in Palladous nitrate or Palladous chloride; The precursor solution of metal Ir is chloro-iridic acid;
Wherein, Polycyclic Aromatic Hydrocarbon Mixture is naphthalene series compound; Mononuclear aromatics mixture comprises benzene, toluene, ethylbenzene, dimethylbenzene, C9 aromatic and C10 aromartic;
FAU type zeolite and at least one molecular sieve be selected from MOR, BEA, MFI or MCM-22 be sodium weight content lower than 2% Hydrogen or ammonium type zeolite.
2. polycyclic aromatic hydrocarbons according to claim 1 is converted into the method for mononuclear aromatics, the amount that it is characterized in that FAU type zeolite by weight percentage in mixture is 50 ~ 90%, and the amount being selected from least one molecular sieve in MOR, BEA, MFI or MCM-22 is 10 ~ 50%.
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| CN104549465B (en) * | 2013-10-28 | 2017-07-14 | 中国石油化工股份有限公司 | Heavy aromatics lightening catalyst of voluminous dimethylbenzene and preparation method thereof |
| CN104549456B (en) * | 2013-10-28 | 2017-01-25 | 中国石油化工股份有限公司 | Heavy aromatic lightening catalyst and preparation method thereof |
| US11001765B2 (en) | 2016-02-25 | 2021-05-11 | Sabic Global Technologies B.V. | Process for combined hydrodesulfurization and hydrocracking of heavy hydrocarbons |
| CN108699449A (en) * | 2016-03-01 | 2018-10-23 | 沙特基础工业全球技术有限公司 | Method for producing mononuclear aromatics by the hydrocarbon charging comprising polycyclic aromatic hydrocarbon |
| CN109694726B (en) * | 2017-10-24 | 2021-07-09 | 中国石油化工股份有限公司 | Catalytic conversion method for increasing yield of propylene and light aromatic hydrocarbon |
| CN109694728B (en) * | 2017-10-24 | 2021-07-09 | 中国石油化工股份有限公司 | Catalytic conversion method of inferior raw oil |
| CN112657539B (en) * | 2019-10-15 | 2023-04-07 | 中国石油化工股份有限公司 | Selective hydrocracking catalyst for polycyclic aromatic hydrocarbon and preparation method and application thereof |
| US11377609B2 (en) | 2019-10-30 | 2022-07-05 | Saudi Arabian Oil Company | System and process for steam cracking and PFO treatment integrating hydrodealkylation and naphtha reforming |
| US11001773B1 (en) | 2019-10-30 | 2021-05-11 | Saudi Arabian Oil Company | System and process for steam cracking and PFO treatment integrating selective hydrogenation and selective hydrocracking |
| US11220637B2 (en) | 2019-10-30 | 2022-01-11 | Saudi Arabian Oil Company | System and process for steam cracking and PFO treatment integrating selective hydrogenation and FCC |
| US11091709B2 (en) | 2019-10-30 | 2021-08-17 | Saudi Arabian Oil Company | System and process for steam cracking and PFO treatment integrating selective hydrogenation, ring opening and naphtha reforming |
| US11091708B2 (en) | 2019-10-30 | 2021-08-17 | Saudi Arabian Oil Company | System and process for steam cracking and PFO treatment integrating selective hydrogenation and ring opening |
| US11220640B2 (en) | 2019-10-30 | 2022-01-11 | Saudi Arabian Oil Company | System and process for steam cracking and PFO treatment integrating selective hydrogenation, FCC and naphtha reforming |
| US11390818B2 (en) | 2019-10-30 | 2022-07-19 | Saudi Arabian Oil Company | System and process for steam cracking and PFO treatment integrating hydrodealkylation |
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