CN103059916A - Method for selective hydrogenation and desulfuration of light cycle oil - Google Patents
Method for selective hydrogenation and desulfuration of light cycle oil Download PDFInfo
- Publication number
- CN103059916A CN103059916A CN2011103254082A CN201110325408A CN103059916A CN 103059916 A CN103059916 A CN 103059916A CN 2011103254082 A CN2011103254082 A CN 2011103254082A CN 201110325408 A CN201110325408 A CN 201110325408A CN 103059916 A CN103059916 A CN 103059916A
- Authority
- CN
- China
- Prior art keywords
- light cycle
- oil
- catalyzer
- hydrogen
- aromatic hydrocarbons
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a method for selective hydrogenation and desulfuration of light cycle oil, and the method is mainly used for solving the problem of high loss of aromatic hydrocarbons in the process of hydrogenation and desulfuration. The technical scheme adopted by the invention is as follows: according to the method, hydrogen and light cycle oil with the sulfur content of 2000-15000ppm, which are used as raw materials, are contacted with a catalyst for reaction under the condition that the volume ratio of hydrogen to oil is (300-800):1, the temperature is 250-450 DEG C, the weight space velocity is 0.5-3h<-1>, and the pressure is 3.0-12.0MPa, wherein after reaction, the naphthalene-series double-ring aromatic hydrocarbon and polycyclic aromatic hydrocarbon in the oil are in a partial saturation or open-loop state, the conversion rate of polycyclic aromatic hydrocarbon (PAH) is up to more than 30.0%, the total aromatics retention of the product is more than 96.0%, the desulfuration rate is more than 96.0%, and the denitrification rate is more than 95.0%, so that the problem in the prior art is better solved and the method can be used in the industrial production of preparation of benzene and dimethylbenzene based on selective hydrogenation of the light cycle oil.
Description
Technical field
The present invention relates to the method for the light cycle oil selective hydrodesulfurization.
Background technology
Catalytic cracking light cycle oil (LCO) mixes use as a kind of second-rate blended diesel component usually with straight-run diesel oil.From the composition of LCO, total aromaticity content is up to 50%～85%, and wherein naphthalene is that double ring arene accounts for about 70%, and mononuclear aromatics and thrcylic aromatic hydrocarbon approximately respectively account for about 15%, and other is alkane, naphthenic hydrocarbon and alkene etc.The sulphur content of LCO is high, and (0.2～1.5wt%), cetane value only has 20～35, and ignition characteristic is poor.China's catalytic cracking (FCC) device year amount of finish surpasses 6,800 ten thousand tons, the year output 10 million ton of LCO.In China, a large amount of LCO call in without hydrotreatment in the total composition of diesel oil, cause diesel quality and stability variation.
Thus, the novel process that LCO uses is also arisen at the historic moment, and is constantly developed.But the technique of existing hydrotreatment LCO mostly belongs to energy intensive, the very large Technology of hydrogen-consuming volume, and the 1000L light cycle oil will consume 1500m at least
3H
2, bad adaptability, whether feasible depending on has or not sufficient hydrogen source.
Owing to not only containing a large amount of organosulfurs, nitride in the LCO raw material, also contain simultaneously a large amount of aromatic hydrocarbons, such technique also will expend hydrogen to reduce aromaticity content in the product for improving the product cetane value in unifining process.For this reason, such technique has not only consumed a large amount of expensive hydrogen in unifining process, has also wasted the aromatic hydrocarbon resource of a large amount of recycling high added values simultaneously.
In order to take full advantage of the aromatic hydrocarbon resource among the LCO, improve its added value, developed the novel catalyzing technology that adapts with it.Adopt catalysis LCO hydrocracking-alkylation selectivity transfer to produce the novel process of benzene (B), toluene (T) and dimethylbenzene (X) etc.But the impurity such as a large amount of sulphur, nitrogen have poisoning effect to catalyzer such as follow-up hydrogenation, selective openings among the LCO, must remove through hydrofining technology first.Therefore, remove among the LCO impurity such as a large amount of sulphur, nitrogen and become the further key of Application and Development of LCO.
LCO belongs to diesel oil distillate, and its deep desulfuration difficulty is large.Mainly be because: contain among (1) LCO just like 4,6-dimethyldibenzothiophene (4, the sulphur compound such as 6-DMDBT) because the substituting group space steric effect causes reactive behavior low, the deep desulfuration difficulty is large; (2) H in polycyclic aromatic hydrocarbons and nitrogenous thing and the product in the raw material
2S has restraining effect to deep desulfuration; (3) in the desulfurization removing nitric process, do not allow the transition hydrogenation, because can cause so a large amount of hydrogenation ring-opening reactions, destroyed the purpose of follow-up selective hydrogenation open loop volume increase aromatic hydrocarbons.(4) in hydrogenating desulfurization (HDS) process, keep to greatest extent methyl, to produce to greatest extent dimethylbenzene.Therefore, these sulphur be remove, multi-functional, high reactivity, high-selective and hydrogenating catalyst for refining just must be selected.
US Patent No. 4206036 adopts titanium oxide to make carrier, and behind the load active component, as Hydrobon catalyst (desulfurization, denitrogenation), but this carrier physical strength is low, and specific surface area is little, and expensive, can't industrial application.
US Patent No. 2006/0052235A1 has introduced a kind of employing with mesopore molecular sieve, such as MCM-41 is carrier, Co, Mo are active ingredient, silicone resin is the Hydrobon catalyst of binding agent, this Hydrobon catalyst has the activity of higher hydrogenating desulfurization (HDS)/olefin saturated, but this patent does not provide the absolute activity of HDS, and the poor stability of mesopore molecular sieve, is difficult to long-time running under the hydrogenating desulfurization environment of harshness.
In order to improve the desulphurizing activated of the low grade oils Hydrobon catalysts such as LCO, adopted W, Ni and the strongly-acid molecular sieve more than the 25m% as active ingredient such as US4820403 and US4971680, CN1302847A has also adopted similar method, owing to adding a large amount of strongly-acid zeolite molecular sieves and strong hydrogenation nickel, tungsten isoreactivity component in the carrier, greatly strengthened the cracking activity of catalyzer, cause the reactions such as a large amount of aromatic hydrocarbons generation open loops, cracking in the oil product, consume a large amount of hydrogen, be unfavorable for the recycling of a large amount of aromatic components in the oil product, be difficult to improve its added value.CN1355273 selects Hydrobon catalyst take catalytic cracking diesel oil as raw material, has adopted novel process, and part has reduced the hydrogen consumption, but distillate aromatic hydrocarbons behind hydrogenation desulfurization and denitrogenation loses by weight percentage greater than 25%.As from the foregoing, adopt above-mentioned traditional catalyst or method to destroy in the low grade oils (LCO, diesel oil) in a large number the aromatic hydrocarbon resource that further processing and utilization improves its added value.
Summary of the invention
Technical problem to be solved by this invention is that existing the light cycle oil hydrogenating desulfurization, the denitrification activity that exist in unifining process are low, and the problem that the aromatic hydrocarbons loss amount is large provides a kind of hydrodesulfurizationprocess process of the highly selective for light cycle oil.The method has hydrogenating desulfurization, denitrification activity is high, the advantage that the aromatic hydrocarbons loss amount is little.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of light cycle selective hydrodesulfurization method, take sulphur content 2000～15000ppm light cycle oil and hydrogen as raw material, wherein the volume ratio of hydrogen/oil is 300～800: 1, be 250～450 ℃ in temperature, weight space velocity is 0.5～3 hour
-1Pressure is under 3.0～12.0MPa condition, raw material contacts with catalyzer, the polycyclic aromatic hydrocarbons of oil product after the reaction, and namely naphthalene is double ring arene and condensed-nuclei aromatics fractional saturation or open loop, by weight percentage, its polycyclic aromatic hydrocarbons transformation efficiency reaches more than 30.0%, and the total aromatic hydrocarbons retention rate of product is greater than 96.0%, desulfurization＞96.0%, denitrogenation＞95.0%, catalyzer comprise following component by weight percentage: a) 67.0～97.0% complex carrier; With the b that carries thereon) at least a among 1.0～8.0% CoO and the NiO; C) 2.0～25.0% MoO
3Wherein complex carrier comprises following component by weight percentage: a) 82.0～99.8%Al
2O
3B) 0.10～8.0%B
2O
3C) 0.10～10.0%P
2O
5
In the catalyzer complex carrier of technique scheme, B
2O
3The source is selected from least a of boric acid, trimethyl borate, ammonium borate; P
2O
5The source is selected from least a of phosphoric acid, ammonium hydrogen phosphate, primary ammonium phosphate; The catalyzer complex carrier adopts the soluble salt solution of formed alumina dipping phosphorus, boron, or adds the soluble salt solution moulding of phosphorus, boron in the aluminum oxide moulding process, drying, roasting and get.
Polycyclic aromatic hydrocarbons transformation efficiency (by weight percentage) calculation formula is as follows:
The total aromatic hydrocarbons retention rate of product (by weight percentage) calculation formula is as follows:
It is the carrier main component that the present invention adopts aluminum oxide, the soluble compound of dipping P, B, by techniques such as load, drying, roastings, or in the aluminum oxide moulding process, add the soluble salt of phosphorus, boron, the technique such as drying, roasting prepares complex carrier, improved the acidity of catalyzer, improve the over-all properties of catalyzer, after load C o, Ni, the Mo isoreactivity component, carrier and active ingredient have produced moderate interaction, catalyzer easily vulcanizes, and has produced the high reactivity position that can be used in a large number desulfurization, denitrogenation after the sulfuration, has desulfurization, characteristics that denitrification activity is high.Because Co, Ni, Mo have relatively moderate hydrogenation activity, therefore reduced the ratio of aromatic hydrocarbons open loop and excessive hydrogenation formation saturated rings alkane in the raw material, improved the aromatic hydrocarbons retention rate.
Using the method for the light cycle oil selective hydrodesulfurization of the present invention, is 300～800: 1 in the volume ratio of hydrogen and light cycle oil, is 250～450 ℃ in temperature, and weight space velocity is 0.5～3 hour
-1Pressure is under 3～12MPa condition, raw material contacts with catalyzer, can make the sulphur content in the light cycle oil remove by weight percentage more than 96.0% after the reaction, denitrification percent is greater than 95.0% by weight percentage, and the total retention rate of aromatic hydrocarbons is by weight percentage greater than 96.0% in the product, and naphthalene is double ring arene and condensed-nuclei aromatics fractional saturation or open loop simultaneously, greater than more than 30%, obtained preferably technique effect at the transformation efficiency of product polycyclic aromatic hydrocarbons.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
The preparation of complex carrier: A: get boehmite 200.0 grams; B: water intaking 40 grams, add the aqueous solution 10.0 grams that contain by weight percentage nitric acid 30%, mixed dissolution is even.B is slowly added A and stir, mediate after 40 minutes, 100～130 ℃ of dryings are 3 hours behind the extruded moulding, 500 ℃ of roastings 2 hours, both γ-Al
2O
3Shaping carrier 1.Get shaping carrier (I) 94.0 grams and contain 3.75%B with weight percent
2O
3Ammonium borate aqueous solution 80.0 gram dipping, afterwards in 100～130 ℃ of dryings 3 hours, 590 ℃ of roastings 2 hours; Carrier contains 3.75%P again with weight percent after the roasting
2O
5Phosphate aqueous solution 80 gram dipping, afterwards in 100～130 ℃ of dryings 3 hours, 550 ℃ of roastings 2 hours, both complex carrier, its composition and raw material sources see Table 1.
Preparation catalyst is adopted in the catalyzer preparation, the steeping fluid preparation, take by weighing cobaltous dihydroxycarbonate 5.5 grams, nickelous nitrate 2.5 grams, adding citric acid 7.6 grams, water 60.0 grams, heating for dissolving, after add quadrol 20.0 gram, add again ammonium molybdate 20.0 grams and be stirred to fully dissolving, take by weighing 80.0 gram complex carrier I, steeping fluid evenly is sprayed on the carrier, had both got Hydrobon catalyst after the drying roasting.The active ingredient formation sees Table 2 in the catalyzer.
Catalyst activity is estimated, and appreciation condition: (1) presulfiding of catalyst: vulcanizing agent is for containing 3.0%CS
2The cyclohexane solution of (weight percent meter), hydrogen to oil volume ratio 500: 1, implantation temperature is 150 ℃, per hour heat up 10 ℃, constant temperature is 4 hours when being warmed up to 230 ℃, continues with per hour 10 ℃ of intensifications, to 290 ℃ of constant temperature 4 hours, continue again with per hour 10 ℃ of intensifications, to 370 ℃ of constant temperature 5 hours; (2) reaction conditions: weight space velocity 1.0 hours
-1, pressure 5.0MPa, hydrogen to oil volume ratio 400: 1,360 ℃ of temperature; (3) reaction raw materials: total sulfur content 0.86% (8600ppm), total nitrogen content 0.035% (350ppm), aromatic hydrocarbons total content 75.2%, (by weight percentage).
Evaluation result sees Table 3.
[embodiment 2～9]
The complex carrier preparation method is identical with enforcement 1 example, and just used steeping fluid material concentration is different in the complex carrier preparation process, and the condition of change sees Table 1.The preparation method of catalyzer is with to implement 1 example identical, just when active ingredient be NiO or CoO when adding NiO, the cobalt salt in the steeping fluid is partly or entirely substituted with nickel salt, the amount of the activity group of load is different on the while complex carrier, specifically sees Table 2.The catalyst activity appreciation condition is with embodiment 1, and evaluation result sees Table 3.
[embodiment 10]
The preparation of complex carrier: A: get boehmite 190.0 grams; B: water intaking 100 grams add and are equivalent to contain B
2O
3Amount 4 gram ammonium borate stirring and dissolving add and are equivalent to contain P
2O
5The phosphoric acid of amount 6 grams, mixed dissolution is even.B is slowly added A and stir, mediate after 40 minutes, 100～130 ℃ of dryings are 3 hours behind the extruded moulding, 500 ℃ of roastings 2 hours, both γ-Al
2O
3Complex carrier.The preparation method of catalyzer is identical with enforcement 1 example, and is just different when the amount of active ingredient, specifically sees Table 2.The catalyst activity appreciation condition is with [embodiment 1], and evaluation result sees Table 3.
[embodiment 11～13]
The complex carrier preparation method is identical with enforcement 10 examples, just adds P in the complex carrier preparation process
2O
5And B
2O
3The kind of precursor material and amount are different, and the condition of change sees Table 1.The preparation method of catalyzer is with to implement 1 example identical, just when active ingredient be NiO or CoO when adding NiO, the cobalt salt in the steeping fluid is partly or entirely substituted with nickel salt, the amount of the active ingredient of load is different on the while complex carrier, specifically sees Table 2.The catalyst activity appreciation condition is with embodiment 1, and evaluation result sees Table 3.
Table 1
* wt% represents weight percent.
Table 2
| Active ingredient | Complex carrier (wt%) | CoO(wt％) | NiO(wt％) | MoO 3(wt％) | CaO(wt％) |
| Embodiment 1 | 80.0 | 4.0 | 1.0 | 15.0 | -- |
| Embodiment 2 | 96.9 | 1.0 | -- | 2.0 | 0.1％ |
| Embodiment 3 | 83.0 | 2.0 | 1.0 | 14.0 | -- |
| Embodiment 4 | 77.0 | -- | 3.0 | 20.0 | -- |
| Embodiment 5 | 68.0 | 3.0 | 4.0 | 25.0 | -- |
| Embodiment 6 | 76.0 | 4.0 | 4.0 | 16.0 | -- |
| Embodiment 7 | 82.0 | 2.0 | 1.0 | 15.0 | -- |
| Embodiment 8 | 76.0 | 1.0 | 5.0 | 18.0 | -- |
| Embodiment 9 | 67.0 | 8.0 | -- | 25.0 | -- |
| Embodiment 10 | 80.0 | 4.0 | 1.0 | 15.0 | -- |
| Embodiment 11 | 67.0 | 8.0 | -- | 25.0 | -- |
| Embodiment 12 | 90.0 | 1.0 | 7.0 | 2.0 | -- |
| Embodiment 13 | 78.0 | 1.0 | 4.0 | 18.0 | -- |
| Comparative example 1 | 80.0 | 4.0 | 1.0 | 15.0 | -- |
| Comparative example 2 | 80.0 | 4.0 | 1.0 | 15.0 | -- |
* wt% represents weight percent.
[comparative example 1]
It is raw material that comparative example 1 carrier adopts aluminum oxide, does not add the components such as boron, phosphorus, and in addition, the preparation method of its carrier and catalyzer is with to implement 1 example identical, and comparative example carrier and catalyzer form and see Table respectively 1 and table 2.
[comparative example 2]
Comparative example 2 carriers adopt aluminum oxide and add by weight percentage 6.0% B
2O
3Be plural components, but do not add phosphorus component, in addition, the preparation method of complex carrier and catalyzer is identical with enforcement 1 example.Comparative example carrier and catalyzer form and see Table respectively 1 and table 2.
Reaction result sees Table 3.
Table 3
* wt% represents weight percent.
[embodiment 14～19]
Select the catalyzer of embodiment 1, see Table 4 with different sulphur content LCO raw materials compositions, under different examination conditions, check and rate, specifically check and rate condition and reaction result is listed in table 5.
Table 4
| Sulphur content (ppm) | Nitrogen content (ppm) | Polycyclic aromatic hydrocarbon content (wt%) | Aromatic hydrocarbons total content (wt%) | |
| Raw material 1 | 2000 | 350 | 45.5 | 72.6 |
| Raw material 2 | 4000 | 260 | 48.3 | 78.3 |
| Raw material 3 | 6000 | 530 | 52.6 | 80.6 |
| Raw material 4 | 8000 | 420 | 56.3 | 77.2 |
| Raw material 5 | 10000 | 760 | 48.7 | 85.3 |
| Raw material 6 | 15000 | 620 | 58.9 | 80.6 |
* wt% represents weight percent.
Table 5
* wt% represents weight percent.
Claims (3)
1. light cycle selective hydrodesulfurization method, take sulphur content 2000～15000ppm light cycle oil and hydrogen as raw material, wherein the volume ratio of hydrogen/oil is 300～800: 1, is 250～450 ℃ in temperature, weight space velocity is 0.5～3 hour
-1Pressure is under 3.0～12.0MPa condition, raw material contacts with catalyzer, the polycyclic aromatic hydrocarbons of oil product after the reaction, and namely naphthalene is double ring arene and condensed-nuclei aromatics fractional saturation or open loop, by weight percentage, its polycyclic aromatic hydrocarbons transformation efficiency reaches more than 30.0%, and the total aromatic hydrocarbons retention rate of product is greater than 96.0%, desulfurization＞96.0%, denitrogenation＞95.0%, catalyzer comprise following component by weight percentage:
A) 67.0～97.0% complex carrier; With carry thereon
B) at least a among 1.0～8.0% CoO and the NiO;
C) 2.0～25.0% MoO
3
Wherein complex carrier comprises following component by weight percentage:
a)82.0～99.8％Al
2O
3；
b)0.10～8.0％B
2O
3；
c)0.10～10.0％P
2O
5。
2. light cycle selective hydrodesulfurization method according to claim 1 is characterized in that in the catalyzer complex carrier B
2O
3The source is selected from least a of boric acid, trimethyl borate, ammonium borate; P
2O
5The source is selected from least a of phosphoric acid, ammonium hydrogen phosphate, primary ammonium phosphate.
3. light cycle selective hydrodesulfurization method according to claim 1, it is characterized in that the catalyzer complex carrier adopts the soluble salt solution of formed alumina dipping phosphorus, boron, or in the aluminum oxide moulding process, add the soluble salt solution moulding of phosphorus, boron, drying, roasting and get.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110325408.2A CN103059916B (en) | 2011-10-24 | 2011-10-24 | Method for selective hydrogenation and desulfuration of light cycle oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110325408.2A CN103059916B (en) | 2011-10-24 | 2011-10-24 | Method for selective hydrogenation and desulfuration of light cycle oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103059916A true CN103059916A (en) | 2013-04-24 |
| CN103059916B CN103059916B (en) | 2015-05-13 |
Family
ID=48102821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110325408.2A Active CN103059916B (en) | 2011-10-24 | 2011-10-24 | Method for selective hydrogenation and desulfuration of light cycle oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103059916B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104148082A (en) * | 2013-05-16 | 2014-11-19 | 中国石油化工股份有限公司 | Preparation method and applications of hydrofining catalyst |
| CN109988634A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | Residual hydrocracking and hydrofinishing group technology |
| CN114433214A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Composite carrier and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302847A (en) * | 2000-01-04 | 2001-07-11 | 中国石油化工集团公司 | Catalyst for hydrotransforming diesel oil and its preparing process |
| CN1769387A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | Diesel fuel fraction hydrotreating method |
| CN1778873A (en) * | 2004-11-26 | 2006-05-31 | 中国石油天然气股份有限公司 | Inferior diesel oil hydrotreating catalyst |
| CN101070488A (en) * | 2006-05-13 | 2007-11-14 | 林方 | Hydrogenation refining catalyst, preparing method and use |
| CN101147871A (en) * | 2006-09-20 | 2008-03-26 | 中国石油化工股份有限公司上海石油化工研究院 | Nickel catalyst for selective hydrogenation |
-
2011
- 2011-10-24 CN CN201110325408.2A patent/CN103059916B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302847A (en) * | 2000-01-04 | 2001-07-11 | 中国石油化工集团公司 | Catalyst for hydrotransforming diesel oil and its preparing process |
| CN1769387A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | Diesel fuel fraction hydrotreating method |
| CN1778873A (en) * | 2004-11-26 | 2006-05-31 | 中国石油天然气股份有限公司 | Inferior diesel oil hydrotreating catalyst |
| CN101070488A (en) * | 2006-05-13 | 2007-11-14 | 林方 | Hydrogenation refining catalyst, preparing method and use |
| CN101147871A (en) * | 2006-09-20 | 2008-03-26 | 中国石油化工股份有限公司上海石油化工研究院 | Nickel catalyst for selective hydrogenation |
Non-Patent Citations (1)
| Title |
|---|
| 张登前 等: "加氢脱氮催化剂及反应机理研究进展", 《现代化工》, 30 June 2007 (2007-06-30) * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104148082A (en) * | 2013-05-16 | 2014-11-19 | 中国石油化工股份有限公司 | Preparation method and applications of hydrofining catalyst |
| CN104148082B (en) * | 2013-05-16 | 2016-12-28 | 中国石油化工股份有限公司 | The Preparation method and use of Hydrobon catalyst |
| CN109988634A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | Residual hydrocracking and hydrofinishing group technology |
| CN109988634B (en) * | 2017-12-29 | 2021-05-04 | 中国石油化工股份有限公司 | Residual oil hydrotreating and hydrofining combined process |
| CN114433214A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Composite carrier and preparation method and application thereof |
| CN114433214B (en) * | 2020-10-19 | 2023-09-29 | 中国石油化工股份有限公司 | Composite carrier and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103059916B (en) | 2015-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101530807B (en) | Preparation method of phosphoric hydrogenation catalyst for realizing deep desulfurization and denitrification | |
| CN102994147B (en) | Method for producing middle distillate oil by medium-pressure hydrocracking of heavy oil | |
| CN109772368A (en) | A kind of high activity hydrogenation and desulphurization catalyst and preparation method thereof | |
| CN102989493A (en) | Preparation method of heavy oil hydrotreating composite catalyst | |
| CN103059916B (en) | Method for selective hydrogenation and desulfuration of light cycle oil | |
| CN104148082B (en) | The Preparation method and use of Hydrobon catalyst | |
| CN103055909B (en) | Catalyst for light cycle oil selective hydrodesulfurization and preparation method thereof | |
| CN1778874B (en) | Hydrogenation dearomatization catalyst containing phosphorus-aluminum molecular sieve | |
| CN102039154B (en) | Hydrogenation sweetening catalyst, preparing method and application thereof | |
| CN104449835A (en) | Cracking C9 and C9+ hydrocarbon hydrogenation method | |
| CN103146420B (en) | Gasoline hydrotreating method | |
| CN101302439A (en) | Hydrocatalyst for preparing fuel by hydrodealkylation of coal-tar pitch and preparation thereof | |
| CN103059917B (en) | Light cycle oil selective hydrorefining method | |
| CN103059983A (en) | Hydrofining catalyst combined filling method | |
| CN102423712B (en) | Preparation method of high-activity inferior diesel oil hydrorefining catalyst | |
| CN102373078A (en) | Deep hydrodesulfurization method for diesel oil | |
| CN105562019B (en) | The catalyst of mercaptan thioetherification | |
| CN103055936B (en) | Light cycle oil selective hydrorefining catalyst and preparation method thereof | |
| CN102614909A (en) | Hydrodenitrogenation catalyst capable of removing nitrogen-containing compound from coal tar, and preparation method and application thereof | |
| CN102827631A (en) | Hydrogenation pretreatment method of mixed wax oil | |
| CN103120945B (en) | Catalyst for hydrofining inferior oil product and preparation method thereof | |
| CN106890660A (en) | Hydrodesulfurization catalyst and preparation method thereof | |
| CN112691681B (en) | Aromatic-rich light distillate selective hydrogenation catalyst, and preparation method and application thereof | |
| CN103122258B (en) | Method for desulfuration by selective hydrogenation of light cycle oil | |
| CN100457863C (en) | Low-temperature hydrogenation catalyst for middle-low distillate oil and preparation and use methods thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |