CN106140293A - A kind of catalyst for coal tar hydrogenation modification and preparation method thereof - Google Patents
A kind of catalyst for coal tar hydrogenation modification and preparation method thereof Download PDFInfo
- Publication number
- CN106140293A CN106140293A CN201510187542.9A CN201510187542A CN106140293A CN 106140293 A CN106140293 A CN 106140293A CN 201510187542 A CN201510187542 A CN 201510187542A CN 106140293 A CN106140293 A CN 106140293A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- coal tar
- kaolin
- modification
- active metal
- 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.)
- Pending
Links
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of catalyst for coal tar hydrogenation modification and preparation method thereof, described catalyst is made up of active metal component, cocatalyst component and carrier, wherein, active metal component is one or more metallic elements in Ni, Mo, Co and W, and cocatalyst component is P2O5And one or more metallic elements in Fe and Mn, carrier is the Kaolin of phosphoric acid modification；Counting the weight of the active metal component 10-30% as vehicle weight with oxide, count the weight of metallic element in the cocatalyst component 3-7% as vehicle weight with oxide, the consumption of phosphoric acid is 1～4 times of vehicle weight.The hydrogenation catalyst of the present invention not only has good hydrodesulfurization, denitrogenation, degumming matter activity, the most also has stronger aromatic saturation and ring opening ability.
Description
Technical field
The present invention relates to a kind of catalyst for coal tar hydrogenation modification, particularly relate to a kind of coal tar distillate catalyst for hydro-upgrading
And preparation method thereof.
Background technology
Coal tar is the by-product of coal high temperature pyrolysis, and its fluid product has a characteristic of natural crude oil, but and ordinary crude oils
Comparing, its density is big, viscosity is high, sulfur content is high, and especially nitrogen content is high, carbon residue is high, asphalitine is high, therefore quality
Difference, is relatively difficult to processing.Along with consumption and the increasing year by year of domestic imported crude oil ratio day by day of petroleum resources in world wide
Adding, how the succedaneum of Appropriate application this oil of coal tar causes with the fuel oil and other industrial chemicals obtaining high-quality
Increasing attention.
Currently, coal tar oil treatment process is mainly after acid-alkali refining to extract and separates by more domestic coal tar manufacturing enterprises
Go out the chemical substance such as phenol, naphthalene or directly burn or after emulsifying as fuel combustion as low-quality fuel oil, meanwhile, its
Sulfur, nitrogen impurity contained by become SO in combustionX、NOX, and acid-alkali refining process produces large amount of sewage,
Not only deficiency in economic performance, and pollute environment.China is not enough due to petroleum resources, and imported crude oil ratio increases year by year, because of
This, with coal tar as raw oil, use suitable secondary operations means to produce the cleaning fuel suitable with oil product or stone
Oil product, not only has significant economic benefit, also has obvious social benefit simultaneously.In the production of cleaning fuel,
Hydrogen addition technology has the advantage that other technique is incomparable, and its core is exactly hydrogenation catalyst.Evaporate with oil secondary operations
Dividing oil Hydrobon catalyst to compare, catalyst for coal tar hydrogenation modification faces the challenge in terms of following four: one is that oxygen contains
Amount height, the water that deoxidation produces all produces very adverse influence to catalyst activity, stability and intensity；Two be colloid,
Carbon residue content is high, easily promotes catalyst carbon deposition, causes catalysqt deactivation and bed blocking；Three is sulfur, nitrogen content height,
Needing deep hydrogenation denitrogenation, otherwise stability does not reaches requirement；Four is that its diesel oil evaporates containing substantial amounts of aromatic hydrocarbons in coal tar
In point, Cetane number is the lowest, it is desirable to deeply hydrodearomatized, and aromatic hydrocarbons to greatest extent on the premise of as far as possible reducing chain rupture
Saturated and open loop, makes every effort to improve to greatest extent Cetane number, and therefore, catalyst to have suitable acidity.
CN1464031A describes a kind of coal tar hydrorefining with Mixture of alumina and titania as carrier and modification
Catalyst.Hydrobon catalyst adds the mixture after the titanium oxide of 1%-40% (mass percent) with aluminium oxide and makees
Carrier, as active metal component and adds VA race and VIIA with the metal sulfide of VIII and VIB such as molybdenum, nickel, cobalt
Some nonmetalloid of race is auxiliary agent.Catalyst compositing range and physico-chemical property are shown in Table 1.And its catalyst for hydro-upgrading
The mixture of the titanium oxide then adding 1%-20% (mass percent) with aluminium oxide makees carrier, with molybdenum, nickel, cobalt, tungsten
It is active metal component Deng the metal sulfide of VIII and VIB and adds VA race and some nonmetalloid of VIIA race is
Auxiliary agent, adds the molecular sieve of 5%-30% (mass percent) as promoter in catalyst for hydro-upgrading.Hydrogenation
Compositing range and the physico-chemical property of modifying catalyst are shown in Table 2.Its method for preparing catalyst uses saturated spray or saturated dipping
Method.
Hydrogenation technique parameter used in CN1464031A: hydrogenation reactor inlet pressure is not more than 15.0Mpa (hydrogen dividing potential drop),
Initial reaction temperature, 370-390 DEG C (beds mean temperature), volume space velocity 0.4-4.0h-1, hydrogen-oil ratio 500-3000
Nm3/m3。
The physico-chemical property of table 1 Hydrobon catalyst
| Title | Coal tar hydrorefining catalyst |
| Chemical composition, % (quality) | |
| MoO3 | 5.0-20.0 |
| NiO | 1.0-10.0 |
| P | 0.1-5.0 |
| TiO2 | 1%-40% |
| Al2O3 | Surplus |
| Physical property | |
| Specific surface, m2/g | 70-260 |
| Pore volume, ml/g | 0.20-0.80 |
| Crushing strength, N/cm | <10 |
| Outward appearance | Ball, microsphere, bar, ring etc. |
| Commercial plant bulk density, kg/m3 | 500-1100 |
The physico-chemical property of table 2 catalyst for hydro-upgrading
| Title | Catalyst for coal tar hydrogenation modification |
| Chemical composition, % (quality) | |
| MoO3 | 5.0-20.0 |
| WO3 | 10-30 |
| NiO | 1.0-10.0 |
| P | 0.1-5.0 |
| TiO2 | 1%-20% |
| Molecular sieve | 5-30% |
| Al2O3 | Surplus |
| Physical property | |
| Specific surface, m2/g | 70-260 |
| Pore volume, ml/g | 0.20-0.80 |
| Crushing strength, N/cm | <15 |
| Outward appearance | Ball, microsphere, bar, ring etc. |
| Commercial plant bulk density, kg/m3 | 500-1100 |
In coal tar hydrogenation modification technique described by CN1464031A and catalyst, hydrofining and hydro-upgrading catalysis
Agent carrier all adds part titanium dioxide component, owing to the pore volume of titanium dioxide own, aperture, specific surface area are less, leads
Cause catalyst pore volume, specific surface area and aperture less than normal, and predominantly macromole aromatic hydrocarbons, colloid and drip in coal tar oil composition
Blue or green matter, the structure of the most above-mentioned catalyst is unfavorable for the diffusion of reactant molecule, and the diffusion rate of reactant is at very great Cheng
Determining reaction rate on degree, therefore the performance of catalyst activity is restricted.Reaction temperature is higher, for 370-385 DEG C.
CN1706917A describes the coal tar hydrogenating diesel catalytic converter of a kind of point of two-stage, including firsts and seconds catalyst,
One stage catalyzing dose is hydrotreating desulfurization and denitrogenation cracking catalyst, and its component and proportioning (weight ratio) thereof be: molybdenum oxide 3-8%,
Cobalt oxide 2-5%, nickel oxide 3-6%, remaining is the carborundum of 40-50nm for granularity；Described hydrogenation desulfurization and denitrogenation
The specific surface area of Cracking catalyst is 180 250m2/ g, pore volume is 1.0-1.2ml/g；Second catalyst is for adding
Hydrogen degree of depth dearomatization catalyst, its component and proportioning (weight ratio) thereof be: platinum 3 5%, palladium 2 5%, remaining
For the carborundum that granularity is 40 50nm；The specific surface area of described hydrotreating deep dearomatizition catalyst is 180 250m2/ g,
Pore volume is 0.6-0.8ml/g.Carborundum can use sol-gal process to produce, and hydrogenation desulfurization and denitrogenation cracking and the degree of depth take off
Virtue catalyst then uses infusion process to prepare.
Two-stage catalyst described by CN1706917A all use carborundum as carrier cause catalyst pore volume, specific surface area and
Aperture is less than normal, and predominantly macromole aromatic hydrocarbons, colloid and asphalitine, the knot of the most above-mentioned catalyst in coal tar oil composition
Structure is unfavorable for the diffusion of reactant molecule, and the diffusion rate of reactant determines reaction rate to a great extent, therefore urges
The performance of agent activity is restricted.Secondly, the acidity of catalyst is relatively low, and affect catalyst is hydrocracked function, no
It is beneficial to tar macromolecular cleavage, is easily caused catalysqt deactivation.Additionally, second catalyst active component uses noble metal, lead
Cause catalyst cost to be greatly increased.
Summary of the invention
The present invention provides a kind of dead oil catalyst for hydro-upgrading and preparation method thereof, and the catalyst of the present invention overcomes
The existing the most high deficiency of catalyst for hydrorefining distillate oil activity, not only has suitable pore volume, aperture, hydrogenation center
And acid centre, and have preferable mechanical strength and water-resistance, can effectively remove coal tar fraction under hydroconversion condition
In sulfur impurity, nitrogen, colloid and asphalitine, saturated aromatic component make part aromatic hydrocarbons open loop.
The catalyst for coal tar hydrogenation modification of the present invention is made up of active metal component, cocatalyst component and carrier, wherein,
Active metal component is one or more metallic elements in Ni, Mo, Co and W, and cocatalyst component is P2O5
And one or more metallic elements in Fe and Mn, carrier is the Kaolin of phosphoric acid modification；
Wherein, in terms of oxide, the weight of active metal component is the 10-30% of vehicle weight, preferably 15-20%；
Such as, in terms of oxide, the weight of W and/or Mo is the 13～17% of vehicle weight, and the weight of Co and/or Ni
3-7% for vehicle weight；
In terms of oxide, the weight of the metallic element in cocatalyst component is the 3-7% of vehicle weight；
The consumption of phosphoric acid is 1～4 times of vehicle weight.
The present invention uses phosphoric acid to be modified Kaolin, and a part of phosphoric acid is as synthesis SAPO (silicon phosphorus aluminum) Series Molecules sieve
Phosphorus source, a part of phosphoric acid is as the P of cocatalyst component2O5Source.
The preparation method of the catalyst for hydro-upgrading of the present invention includes:
(1) Modification of kaolin
Kaolin is calcined by the present invention and acid dip processes and prepares alukalin, as the carrier of hydrogenation catalyst.
Concrete operations are as follows:
A. high-temperature calcination
By Kaolin in air atmosphere, temperature be to calcine 2-7h in the Muffle furnace of 500 800 DEG C, then natural
Cooling；
B. phosphoric acid processes
By the Kaolin after calcining, under 60 90 DEG C of water-baths, impregnate 4 with the phosphoric acid solution that concentration is 1-4mol/L
9h, dipping terminates rear aging 1-5h；
C. it is dried
Kaolin after step b is processed in air atmosphere, temperature be that the baking oven of 90 110 DEG C is dried 10-14
H, obtains the Kaolin of phosphoric acid modification；
(2) prepared by catalyst
The present invention catalyst preparation with the Kaolin of phosphoric acid modification as presoma specifically comprises the following steps that
D. tetraethyl orthosilicate (TEOS) is joined in modified Kaolin, tetraethyl orthosilicate and kaolinic weight ratio
It is 1:5；Under 40-80 DEG C of water bath condition, it is stirred 2-6h, whipping process adds in Fe and Mn
Plant or the complex of various metals；In system, the one in di-n-propylamine and diisopropylamine is added in whipping process
Or multi-solvents is as the template of synthesis SAPO molecular sieve, described solvent and kaolinic weight ratio are 1～3:10；
E. the slaine of active metal component is configured to the aqueous solution that total concentration is 5 25wt%, and by the gold of preparation
Belong to saline solution join in the serosity that Step d obtains, then by mixed liquor at 40 80 DEG C in water-bath aging 2～
6h, is loaded in autoclave reacting 8-14h in 130 200 DEG C afterwards；Through filtration treatment, will collect
The solid arrived is dried 6～9h at 90-130 DEG C, obtains catalyst precursor；
F. the catalyst precursor obtained by step e is calcined 1-4h through 550 800 DEG C under air atmosphere,
I.e. prepare catalyst for hydro-upgrading；
Further, the preparation method of the catalyst for hydro-upgrading of the present invention also includes:
G. the catalyst for hydro-upgrading obtained by step f is before hydrogenation reaction, processes through presulfurization.
Wherein, in step d, use the complex of the diethylenetriamine pentacarboxylic acid of Fe and/or Mn, select divinyl three
Amine pentacarboxylic acid is 1:1 as chelating agent, this chelating agent with the mol ratio of Fe or Mn.
In step g, using wet method presulfurization in catalyst device, sulfurized oil is aerial kerosene, and vulcanizing agent uses dimethyl
Disulfide.
In step e, the slaine of active metal component can be cobalt nitrate, nitric acid molybdenum, ammonium metatungstate, nickel nitrate, also
Other soluble metallic salts of active metal component can be used.
Present invention also offers described catalyst for coal tar hydrogenation modification purposes in coal tar hydrogenation modification.
The present invention is with phosphoric acid modification Kaolin as carrier, and phosphoric acid can just introduce system as phosphorus source when Modification of kaolin,
And promoter metal enters the skeleton of the SAPO Series Molecules sieve being grown in kaolin surface in sieve synthesis procedure
In；Complete in the hydro-thermal of Zeolite synthesis step and active metal is immersed in a step, with selected from Ni, Mo, Co and W
In one or more metals be active component, catalyst has stronger acids and cracking open loop ability.
The catalyst for hydro-upgrading of the present invention is applicable to process high-sulfur, high nitrogen, high aromatic hydrocarbons and the coal tar fraction of gum level
Oil, is also applied for other inferior distillate oil, such as catalytic cracking diesel oil, coker gas oil etc..In use, this catalysis
Hydrogenation protecting agent to be installed additional above agent bed.Hydrogenation protecting agent is protective agent commonly used in the art, without particular/special requirement.This
Bright catalyst is when the hydrogenation modifying process of dead oil, and its reaction condition is: reaction temperature 340-390 DEG C,
Hydrogen dividing potential drop 8.0-16.0MPa, hydrogen is 700-1500 with the volume ratio of coal tar, volume space velocity 0.4-1.5 during liquid
h-1, its effect is that hydrodesulfurization rate is not less than 95%, and hydrodenitrogeneration rate is not less than 90%, and liquid yield is not less than 95%.
Detailed description of the invention
The preparation of catalyst
Embodiment 1
By the Kaolin after calcining, with the phosphoric acid solution that concentration is 2mol/L stir process 6h, phosphorus under 60 DEG C of water-baths
Acid consumption is 20mL/g Kaolin.Afterwards by this solution burin-in process 2h under 60 DEG C of water bath condition.After process terminates,
Whole process mixture is directly placed into 12h in 100 DEG C of baking ovens, water is evaporated.Then under 50 DEG C of water bath condition,
Adding tetraethyl orthosilicate in Kaolin after processing again, addition is the 20% of Kaolin quality.It is added thereto to Fe again
The complex of diethylenetriamine pentacarboxylic acid, in terms of oxide, the consumption of Fe is the 3.5% of Kaolin weight, required network
The mole of mixture is 1:1 with the ratio of the mole of Fe.Di-n-propylamine is added again in mixture system, di-n-propylamine
Consumption is the 15% of Kaolin quality.Under 50 DEG C of water bath condition, stir 4h.By cobalt nitrate, nitric acid molybdenum preparation total concentration
For the slaine mixed aqueous solution of Co and Mo of 10wt%, wherein nitric acid molybdenum is 8.5wt%, and cobalt nitrate is 1.5wt%；
By in the metal salt solution addition system of preparation, at 60 DEG C, impregnate 4h.Proceed to afterwards in autoclave 170 DEG C anti-
Answering 8h, being placed in 120 DEG C of baking ovens of filtration is dried 8h, obtains catalyst precursor.Then it is catalyzed in air atmosphere
Agent presoma can be prepared by the catalyst A for hydrogenation through 550 DEG C of calcining 2h.Catalyst before hydrogenation reaction,
Need to process through presulfurization.The present invention uses wet method presulfurization in catalyst device, and sulfurized oil is aerial kerosene, and vulcanizing agent is adopted
Use dimethyl disulfide.
Embodiment 2
By the Kaolin after calcining, with the phosphoric acid solution that concentration is 2mol/L stir process 6h, phosphorus under 60 DEG C of water-baths
Acid consumption is 20mL/g Kaolin.This solution burin-in process 2h under 60 DEG C of water bath condition afterwards.After process terminates,
Whole process mixture is directly placed into 12h in 100 DEG C of baking ovens, is evaporated by water.Then under 50 DEG C of water bath condition, then
Adding tetraethyl orthosilicate in Kaolin after processing, addition is the 20% of Kaolin quality.It is added thereto to Mn again
The complex of diethylenetriamine pentacarboxylic acid, in terms of oxide, the consumption of Mn is the 3.5% of Kaolin quality, required network
The mole of mixture is 1:1 with the ratio of the mole of Mn.Di-n-propylamine is added again in mixture system, di-n-propylamine
Consumption is the 15% of Kaolin quality.Under 50 DEG C of water bath condition, stir 4h.Prepare the denseest with ammonium metatungstate and nickel nitrate
Degree is the slaine mixed aqueous solution of 15wt%Ni and W, and wherein ammonium metatungstate is 13wt%, and nickel nitrate is 2wt%, will
In the metal salt solution addition system of preparation, at 60 DEG C, impregnate 4h.Proceed to 170 DEG C of reactions in autoclave afterwards
8h, being placed in 120 DEG C of baking ovens of filtration is dried 8h, obtains catalyst precursor, then in air atmosphere through 550 DEG C
Calcining 2h can be prepared by the catalyst B for hydrogenation.Catalyst, before hydrogenation reaction, need to process through presulfurization.
The present invention uses wet method presulfurization in catalyst device, and sulfurized oil is aerial kerosene, and vulcanizing agent uses dimethyl disulfide.
Comparative example
The present embodiment is comparative example, with the metal of Co and Mo that cobalt nitrate, nitric acid molybdenum preparation total concentration are 10wt%
Salt mixed aqueous solution, wherein nitric acid molybdenum is 8.5wt%, and cobalt nitrate is 1.5wt%, by metal salt solution and three oxygen of preparation
Change alumina supporter stirring to pulp, and add the P of 5wt%2O5Modifying agent impregnates 4h at 60 DEG C.Proceed to high pressure afterwards anti-
Answer in still 170 DEG C of reaction 8h, filtrations be placed on 120 DEG C of baking ovens in dry 12h, obtain catalyst precursor, so
After air atmosphere through 350 DEG C calcining 2h can be prepared by for hydrogenation catalyst C.Catalyst is for hydrogenation reaction
Before, need to process through presulfurization.Using wet method presulfurization in catalyst device, sulfurized oil is aerial kerosene, and vulcanizing agent uses
Dimethyl disulfide.
Catalyst performance evaluation
With dead oil as raw material, 100ml medium-sized fixed bed hydrogenation device carries out technique to above-mentioned catalyst
Condition evaluating.Catalytic hydrogenation conditions is: reaction temperature 380 DEG C, pressure 12MPa；Volume space velocity 0.4h during liquid-1；
Hydrogen-oil ratio 1600.
Data from table 3 and 4 it can be seen that catalyst prepared by the present invention has higher hydrogenation activity, its sulfur, nitrogen
Removal efficiency is high, and diesel oil distillate Cetane number has a big increase.
The catalytic effect of table 3 catalyst
The catalytic effect of table 4 catalyst
The catalyst of the present invention is with phosphoric acid modification Kaolin as carrier, by water under high pressure full-boiled process by dipping process and Kaolin table
SAPO Series Molecules sieve in face generates Process fusion to be carried out in a step, and adds the metal pair such as Fe and/or Mn of complex state
Carrier is modified so that part Fe and/or Mn can enter framework of molecular sieve and change its acidity.And with selected from Ni,
One or more metals in Mo, Co and W are chief active metal, and catalyst hydrogenation is lived by the addition investigating these metals
The impact of property.
The catalyst that the present invention provides is nucleocapsid structure, the SAPO Series Molecules sieve at kaolin surface growth in situ, and
In such framework of molecular sieve part Si or Al can be replaced by Fe or Mn, and by water under high pressure full-boiled process by dipping process with
Molecular sieve molded process completes in same step, it is ensured that active metallic ion Ni, W or Co, Mo can be uniform low close
Degree is scattered in the outer surface of carrier, and this catalyst has stronger acidity, thus has that higher hydrogenation is saturated and open loop is lived
Property, meanwhile, also there is good cracking performance.Therefore the catalyst that the present invention provides is to macromole in the component of coal tar
Aromatic hydrocarbons, colloid and asphalitine have the highest hydro-upgrading activity.Additionally, sulfur in upgraded products, nitrogen, removal efficiency is high,
Diesel oil distillate Cetane number has a big increase.
Compared with prior art, the hydrogenation catalyst of the present invention not only has good hydrodesulfurization, denitrogenation, degumming matter are lived
Property, the most also there is stronger aromatic saturation and ring opening ability, colm tarry distillate is through catalyst for hydro-upgrading of the present invention
After hydrotreating, can prepare low-sulfur, the high-quality Petroleum of low nitrogen and diesel component, the Cetane number of diesel oil distillate can improve
8-10 unit, liquid yield is more than 95%.Catalyst the most of the present invention also has good stability and mechanical strength.
Claims (10)
1. a catalyst for coal tar hydrogenation modification, it is made up of active metal component, cocatalyst component and carrier,
Wherein, active metal component is one or more metallic elements in Ni, Mo, Co and W, cocatalyst component
For P2O5And one or more metallic elements in Fe and Mn, carrier is the Kaolin of phosphoric acid modification.
Catalyst for coal tar hydrogenation modification the most according to claim 1, wherein, active metal group in terms of oxide
The 10-30% that weight is vehicle weight divided.
Catalyst for coal tar hydrogenation modification the most according to claim 2, wherein, active metal group in terms of oxide
The 15-20% that weight is vehicle weight divided.
Catalyst for coal tar hydrogenation modification the most according to claim 1, wherein, promoter group in terms of oxide
The weight of the metallic element in Fen is the 3-7% of vehicle weight.
Catalyst for coal tar hydrogenation modification the most according to claim 1, wherein, the consumption of phosphoric acid is vehicle weight
1～4 times.
6. a preparation method for the catalyst for coal tar hydrogenation modification described in claim 1, described method includes:
(1) Modification of kaolin
A. by Kaolin in air atmosphere, temperature be to calcine 2-7h, then in the Muffle furnace of 500 800 DEG C
Temperature fall；
B. by the Kaolin after calcining, soak under 60 90 DEG C of water-baths with the phosphoric acid solution that concentration is 1-4mol/L
Stain 4 9h, dipping terminates rear aging 1-5h；
C. the Kaolin after step b being processed in air atmosphere, temperature be that the baking oven of 90 110 DEG C is dried 10-
14h, obtains the Kaolin of phosphoric acid modification；
(2) prepared by catalyst
D. being joined by tetraethyl orthosilicate in modified Kaolin, tetraethyl orthosilicate and kaolinic weight ratio are 1:5；
Under 40 80 DEG C of water bath condition, it is stirred 2 6h, whipping process adds the one in Fe and Mn
Or the complex of various metals；Whipping process adds in system the one in di-n-propylamine and diisopropylamine or
Multi-solvents is as the template of synthesis SAPO molecular sieve, and described solvent and kaolinic weight ratio are 1～3:10；
E. the slaine of active metal component is configured to the aqueous solution that total concentration is 5 25wt%, and by the gold of preparation
Belong to saline solution and join in the serosity that Step d obtains, then by mixed liquor at 40 80 DEG C in water-bath aging 2～6
H, is loaded in autoclave reacting 8-14h in 130 200 DEG C afterwards；Through filtration treatment, will collect
Solid at 90 130 DEG C be dried 6～9h, obtain catalyst precursor；
F. the catalyst precursor obtained by step e is calcined 1-4h through 550 800 DEG C under air atmosphere,
I.e. prepare catalyst for hydro-upgrading.
Method the most according to claim 6, farther includes,
Catalyst for hydro-upgrading obtained by step f, before hydrogenation reaction, processes through presulfurization.
Method the most according to claim 7, wherein, presulfurization processes and uses wet method presulfurization in catalyst device,
Sulfurized oil is aerial kerosene, and vulcanizing agent uses dimethyl disulfide.
9. according to the method according to any one of claim 6-8, wherein, the complex of Fe and Mn is Fe and Mn
Diethylenetriamine pentacarboxylic acid complex.
10. according to utilizing the purposes in coal tar hydrogenation modification of the catalyst according to any one of claim 1-5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510187542.9A CN106140293A (en) | 2015-04-20 | 2015-04-20 | A kind of catalyst for coal tar hydrogenation modification and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510187542.9A CN106140293A (en) | 2015-04-20 | 2015-04-20 | A kind of catalyst for coal tar hydrogenation modification and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106140293A true CN106140293A (en) | 2016-11-23 |
Family
ID=58058627
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510187542.9A Pending CN106140293A (en) | 2015-04-20 | 2015-04-20 | A kind of catalyst for coal tar hydrogenation modification and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106140293A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047051A (en) * | 2017-12-12 | 2018-05-18 | 万华化学集团股份有限公司 | Compound purposes and method of the molecular sieve catalyst for catalytic cracking processing aniline tar |
| CN109569635A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | For Tar production fuel oil hydrogenation catalysts |
| CN109575986A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | Method for Tar production fuel oil |
| CN109701571A (en) * | 2018-12-11 | 2019-05-03 | 南京杰科丰环保技术装备研究院有限公司 | A kind of preparation method of P Modification composite hydrogenation desulphurization catalyst |
| CN109718820A (en) * | 2018-12-11 | 2019-05-07 | 南京杰科丰环保技术装备研究院有限公司 | A kind of P Modification composite hydrogenation desulphurization catalyst |
| CN114425356A (en) * | 2020-09-28 | 2022-05-03 | 中国石油化工股份有限公司 | Hydrogenation catalyst combination and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1110304A (en) * | 1994-04-13 | 1995-10-18 | 中国石油化工总公司 | Heavy oil hydrotreatment catalyst |
| CN101433865A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Residual oil hydrocatalyst carrier and preparation method thereof |
| CN102029157A (en) * | 2010-11-25 | 2011-04-27 | 同济大学 | Catalyst used for coal tar pitch hydrocracking lightening reaction |
| CN104998693A (en) * | 2015-05-26 | 2015-10-28 | 福州大学 | Carrier, inferior oil hydrogenation catalyst based on same and preparing method thereof |
-
2015
- 2015-04-20 CN CN201510187542.9A patent/CN106140293A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1110304A (en) * | 1994-04-13 | 1995-10-18 | 中国石油化工总公司 | Heavy oil hydrotreatment catalyst |
| CN101433865A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Residual oil hydrocatalyst carrier and preparation method thereof |
| CN102029157A (en) * | 2010-11-25 | 2011-04-27 | 同济大学 | Catalyst used for coal tar pitch hydrocracking lightening reaction |
| CN104998693A (en) * | 2015-05-26 | 2015-10-28 | 福州大学 | Carrier, inferior oil hydrogenation catalyst based on same and preparing method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 刘从华等: "改性高岭土性能研究", 《石油炼制与化工》 * |
| 郑淑琴等: "磷改性高岭土型流化催化裂化催化剂的表面酸性及裂化性能的研究", 《现代化工》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109569635A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | For Tar production fuel oil hydrogenation catalysts |
| CN109575986A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | Method for Tar production fuel oil |
| CN109575986B (en) * | 2017-09-28 | 2020-12-29 | 中国石油化工股份有限公司 | Method for producing fuel oil from tar |
| CN109569635B (en) * | 2017-09-28 | 2021-12-28 | 中国石油化工股份有限公司 | Hydrogenation catalyst for producing fuel oil from tar |
| CN108047051A (en) * | 2017-12-12 | 2018-05-18 | 万华化学集团股份有限公司 | Compound purposes and method of the molecular sieve catalyst for catalytic cracking processing aniline tar |
| CN108047051B (en) * | 2017-12-12 | 2020-05-08 | 万华化学集团股份有限公司 | Application and method of compound molecular sieve catalyst in catalytic cracking treatment of aniline tar |
| CN109701571A (en) * | 2018-12-11 | 2019-05-03 | 南京杰科丰环保技术装备研究院有限公司 | A kind of preparation method of P Modification composite hydrogenation desulphurization catalyst |
| CN109718820A (en) * | 2018-12-11 | 2019-05-07 | 南京杰科丰环保技术装备研究院有限公司 | A kind of P Modification composite hydrogenation desulphurization catalyst |
| CN114425356A (en) * | 2020-09-28 | 2022-05-03 | 中国石油化工股份有限公司 | Hydrogenation catalyst combination and application thereof |
| CN114425356B (en) * | 2020-09-28 | 2024-01-30 | 中国石油化工股份有限公司 | Hydrogenation catalyst combination and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106140293A (en) | A kind of catalyst for coal tar hydrogenation modification and preparation method thereof | |
| CN101530807B (en) | Preparation method of phosphoric hydrogenation catalyst for realizing deep desulfurization and denitrification | |
| CN100337747C (en) | Coal tar hydrogenating modification catalyst and its prepn and application | |
| CN101722055B (en) | Method for preparing sulfide type catalyst | |
| RU2402380C1 (en) | Catalyst for hydrofining hydrocarbon material, method of preparing said catalyst and hydrofining process | |
| CN101544904A (en) | Composite metal oxide catalyst, preparation and application thereof | |
| CN101905175B (en) | Method for preparing heavy distillate hydrotreating catalyst | |
| WO2011103698A1 (en) | Hydro refining catalyst | |
| CN102051217A (en) | Hydrogenation method for producing ultra-low sulfur clean diesel | |
| CN106179414B (en) | A kind of sulfurized hydrogenation catalyst for refining and preparation method thereof | |
| CN105733646B (en) | A kind of method of high-grade aliphatic ester Hydrogenation hydrocarbon | |
| CN108273514A (en) | A kind of preparation method with acid non-supported hydrogenation catalyst | |
| CN104888821A (en) | High alkaline nitrogen-containing shale oil hydrogenation upgrading catalyst | |
| CN102041042B (en) | Inferior wax oil hydrotreating method | |
| CN102465011A (en) | Hydrotreatment method of heavy distillate oil | |
| CN103801343B (en) | A kind of preparation method of hydrotreating catalyst | |
| CN112691681B (en) | Aromatic-rich light distillate selective hydrogenation catalyst, and preparation method and application thereof | |
| CN107970958A (en) | A kind of hydrogenation catalyst and its preparation method and application | |
| CN102465027A (en) | Hydrotreating method of heavy distillate oil | |
| RU2626401C1 (en) | Method of hydrotreating hydrocracking feedstock | |
| CN110180585A (en) | A kind of gasoline hydrogenation treatment catalyst and preparation method thereof | |
| CN112705214B (en) | Aromatic-rich heavy distillate selective hydrofining catalyst, preparation method and application | |
| CN103801319A (en) | Hydrotreating catalyst and preparation method thereof | |
| CN106433750A (en) | Hydrogenation desulfurization and denitrification process of diesel oil | |
| CN108795493A (en) | A kind of method of hydrotreating producing clean gasoline |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 102200 Beijing City, Changping District science and Technology Park Chang Huai Lu No. 155 Applicant after: Shenwu science and technology group Limited by Share Ltd Address before: 102200 Beijing city Changping District Machi Town cow Road No. 18 Applicant before: Beijing Shenwu Environment Energy Technology Group Co., Ltd. |
|
| CB02 | Change of applicant information |