CN108855163A - A kind of ten tail oil catalyst for cracking of reformation carbon and its preparation and application - Google Patents
A kind of ten tail oil catalyst for cracking of reformation carbon and its preparation and application Download PDFInfo
- Publication number
- CN108855163A CN108855163A CN201710343287.1A CN201710343287A CN108855163A CN 108855163 A CN108855163 A CN 108855163A CN 201710343287 A CN201710343287 A CN 201710343287A CN 108855163 A CN108855163 A CN 108855163A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carbon
- oil
- tail oil
- cracking
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
- C07C2527/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2527/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- C07C2527/19—Molybdenum
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to technical field of petrochemical industry, especially a kind of ten tail oil catalyst for cracking of reformation carbon and its preparation and application, it include the active ingredient and silicic acid alumina supporter of molybdenum, nickel, cobalt and phosphorus in the catalyst, the silicic acid alumina supporter accounts for the 25-50% of catalyst gross mass, and active ingredient is grouped as by following mass percent group：71-81% molybdenum oxide, 11-21% nickel oxide, 3.5-6.5% cobalt oxide and 1.5-4.5% phosphate compounds.Catalyst provided by the present invention can be applied to reform ten tail oil catalyst for cracking of carbon in reformation ten tail oil of carbon cracking production aromatic solvent, advanced treating is carried out to ten tail oil of carbon is reformed, the density of oil product can be effectively reduced, oil distillation is shifted to low boiling point direction, there is significant lighting effect.Product after adding hydrogen carries out rectifying separation again, and high boiling aromatic hydrocarbon solvent oil generated meets national standard, is of great significance to the reuse ratio and alleviation petroleum resources exhaustion that improve resource.
Description
Technical field
The invention belongs to technical field of petrochemical industry, and in particular to a kind of ten tail oil catalyst for cracking of reformation carbon and its preparation
With application.
Background technique
It is mostly to pass through in its processing at present using the by-product C+10 heavy aromatic hydrocarbon of petroleum catalytic reforming as the manufacturing enterprise of raw material
The products such as the higher high boiling aromatic hydrocarbon solvent of productive value, durol, isodurene, naphthalene, methyl naphthalene after simple rectifying separation,
Then major part is comprehensively utilized heavy constituent tail oil (about 10%-50%) after processed without deep development, only as cheap
Plasticizer or fuel additive use.This had both caused the waste of resource, also produced serious pollution to environment, failed sufficiently to send out
Wave the economic benefit of Heavy Aromatic Hydrocarbons.The ability for the enterprise for having been carried out industrialized production at home at present still is apparent not enough, therefore
How the heavy constituent tail oil of C+10 heavy aromatic hydrocarbon to be cracked, carries out the deep processing of systematization, sufficiently excavate its utility value, become
The key of technique research and development.
Summary of the invention
First of this practical invention is designed to provide a kind of ten tail oil catalyst for cracking of reformation carbon, is urged with solving petroleum
Change reform by-product C+10 heavy aromatic hydrocarbon it is processed after the tail oil of grouping again can not deep development and utilize the problem of.
To achieve the above object, the present invention provides the following technical solutions：A kind of ten tail oil catalyst for cracking of reformation carbon includes
Molybdenum, nickel, cobalt and phosphorus active ingredient and silicic acid alumina supporter, the silicic acid alumina supporter accounts for the 25-50% of catalyst gross mass, institute
Active ingredient is stated to be grouped as by following mass percent group：71-81% molybdenum oxide, 11-21% nickel oxide, 3.5-6.5% oxidation
Cobalt and 1.5-4.5% phosphate compounds.
A second object of the present invention is to provide a kind of preparation methods for reforming ten tail oil catalyst for cracking of carbon, including with
Lower step：
(1) preparation of mixed solution：It takes ammonium molybdate, nickel nitrate, cobalt nitrate and phosphoric acid to be dissolved in distilled water, it is molten to form mixing
Liquid；
(2) it impregnates：Silicic acid alumina supporter is gradually immersed in mixed solution, is impregnated 6-10 hours at room temperature；
(3) it dries：It takes out impregnated carrier to be put into drying box, rises to 110 ± 5 DEG C from room temperature, heating rate 40
± 5 DEG C/h, 110 ± 5 DEG C constant temperature 3 hours；
(4) it roasts：It after drying, is roasted 4 hours in muffle furnace in 450-550 DEG C, needed for being made after natural cooling
Catalyst.
The present invention dissolves active ingredient in the solution in the form of salt, is then impregnated on porous silicic acid alumina supporter simultaneously
It penetrates on inner surface, the catalyst after dipping escapes water evaporation when dry, and the salt of active component is made to be retained in alumina silicate
On the inner surface of carrier, the oxide of stable state is made after heated decomposition, is conducive to storage and transport, after activated when in use
Active component is made, the advantage that active component is scattered, activity is high.
Preferably, the silicic acid alumina supporter according to step (2) the method impregnate 4 times, and every time dipping front and back according to
The drying of step (3) the method, repeated impregnations are to obtain sufficiently large load capacity, so that carrier more fully adsorbs work
Property ingredient.
Preferably, the mass ratio of ammonium molybdate described in step (1), nickel nitrate, cobalt nitrate, phosphoric acid and distilled water is 100：
39-85:14-23:1.5-5:265-275.Preferably, the mass ratio of silicic acid alumina supporter and mixed solution described in step (2)
It is 1:1.6-4.6.
Invention also provides reform ten tail oil catalyst for cracking of carbon to reform ten tail oil of carbon cracking production aromatic solvent
In application, solve the problems, such as that the heavy constituent tail oil of catalytic reforming C+10 heavy aromatic hydrocarbon fails rationally to make full use of.
Concrete operation method is：
(a) hydrocracking：By Catalyst packing into continuous fixed bed reactors, reforms ten tail oil of carbon and pass through fixed bed bed
Layer carries out pre-add hydrogen, hydrocracking and hydrofinishing with hydrogen under 350-385 DEG C, 5.0-9.0MPa Hydrogen Vapor Pressure and is added
Hydrogen product, the hydrogenation products contain benzene,toluene,xylene, trimethylbenzene, durene, penta-methyl benzene, non-aromatic light component and boiling point
220-250 DEG C or more of tail oil；
(b) rectifying separates：Hydrogenation products obtained by step (a) are subjected to rectifying separation, 135 DEG C of front-end volatiles can be used as gasoline
Ready-mixed oil or further isolated No. 6 solvent naphthas and No. 90 solvent naphthas, 135-145 DEG C of fraction are mixed xylenes, 150-180
DEG C fraction is S1000 solvent naphtha, and 178-215 DEG C of fraction is S1500 solvent naphtha, and 210-250 DEG C of fraction is S2000 solvent
Oil；Distillation kettle liquid after 250 DEG C can be mixed with the heavy constituent tail oil of catalytic reforming C+10 heavy aromatic hydrocarbon, re-start plus hydrogen is split
Solution reaction；No. 6 solvent naphtha boiling ranges are 60-90 DEG C, and the boiling range of No. 90 solvent naphthas is 90-120 DEG C；
It include the active ingredient and silicic acid alumina supporter of molybdenum, nickel, cobalt and phosphorus, the silicon in catalyst described in step (a)
Sour alumina supporter accounts for the 25-50% of catalyst gross mass, and the active ingredient is grouped as by following mass percent group：71-81%
Molybdenum oxide, 11-21% nickel oxide, 3.5-6.5% cobalt oxide and 1.5-4.5% phosphorous oxide.
Preferably, the volume space velocity for reforming ten tail oil of carbon is 0.6-2.5/h, and volume hydrogen-oil ratio is 600-2500：1.
Heavy constituent tail oil (component after 220-250 DEG C of boiling range) complicated composition of catalytic reforming C+10 heavy aromatic hydrocarbon, bromine number are inclined
Low, boiling point differs very little between component, and many is high-solidification point, and resource availability is low.The prior art does not carry out it rationally
It utilizes, but is used as plasticizer or fuel additive more, result in waste of resources.The purpose of the present invention is to solve existing
Defect present in technology provides a kind of simple process, convenient for the continuous producing method of industrial operation.
This method with the heavy constituent tail oil (component after 220-250 DEG C of boiling range) of catalytic reforming C+10 heavy aromatic hydrocarbon be raw material,
By being equipped with the continuous fixed bed reactors of catalyst, pre-add hydrogen, hydrocracking and unifining process are carried out, to two and two
The hydrogenated cracking of the aromatic hydrocarbons of a above phenyl ring generates mononuclear aromatics, effectively reduces the density of oil product, by oil distillation to low
The transfer of boiling point direction, has significant lighting effect.Product after adding hydrogen carries out rectifying separation, higher boiling virtue produced again
Hydrocarbon solvent oil meets national standard (GB/T29497-2013), mentions to improve the reuse ratio of resource and alleviating petroleum resources exhaustion
For new effective way.
Preferably, it after the catalyst is packed into reactor, is activated before being passed through reformation ten tail oil of carbon, it is specific to grasp
It is as method：Catalyst is fitted into continuous fixed bed reactors, is passed through hydrogen until system pressure is 3.0-4.0MPa, foundation
Recycle and gradually heat up 150 ± 5 DEG C, with high-pressure pump injection the sulfurized oil containing carbon disulfide, and be gradually warming up to 320 ± 10 DEG C into
Row vulcanization, vulcanization time are 28 hours, and the sulfurized oil is high boiling 1500# solvent naphtha, and the quality of the carbon disulfide is
0.3 times of catalyst quality, vulcanization oil quality are 30 times of catalyst quality.
The active component of catalyst is existing for stable oxidation states.The metal component of these oxidation state is adding hydrogen
Activity in subtractive process is lower, only just there is higher activity when it is converted into sulphided state.The vulcanization of catalyst just refers to
In presence of hydrogen, vulcanizing agent (carbon disulfide) decomposes generates H to catalyst2S, H2S is converted catalyst metal components by oxidation state
At corresponding sulphided state.Sulfurized oil containing carbon disulfide is dissolved in carbon disulfide in high boiling 1500# solvent naphtha, two sulphur
Change 0.3 times that carbon amounts is activation of catalyst quality.
It is further preferred that the air speed of the sulfurized oil containing carbon disulfide is 1.0/h, hydrogen-oil ratio 800:1.
Compared with prior art, the beneficial effects of the invention are as follows：
1, ten tail oil catalyst for cracking of reformation carbon provided by the present invention, it is excellent that concrete activity component is scattered, activity is high
Point.
2, the present invention is using the continuous fixed bed reactors equipped with catalyst to the heavy constituent of catalytic reforming C+10 heavy aromatic hydrocarbon
Tail oil carries out advanced treating, can effectively reduce the density of oil product, and oil distillation is shifted to low boiling point direction, is had significant
Lighting effect.Product after adding hydrogen carries out rectifying separation again, and high boiling aromatic hydrocarbon solvent oil generated meets national standard
(GB/T29497-2013), it is of great significance to the reuse ratio and alleviation petroleum resources exhaustion that improve resource.
Specific embodiment
Below in conjunction with the embodiment of the present invention, the technical solution in the present invention is clearly and completely described, it is clear that
Described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the implementation in the present invention
Example, every other embodiment obtained by those of ordinary skill in the art without making creative efforts belong to
The scope of protection of the invention.
Embodiment 1
(1) preparation of mixed solution：Take 24.17 grams of ammonium molybdate, 20.44 grams of nickel nitrate, 3.40 grams of cobalt nitrate and phosphoric acid
0.37 gram is dissolved in 67 milliliters of distilled water, forms mixed solution；
(2) it impregnates：25.08 grams of carriers of alumina silicate are gradually immersed in mixed solution obtained by step (1), are impregnated at room temperature
8 hours；
(3) it dries：It takes out impregnated carrier to be put into drying box, rises to 115 DEG C from room temperature, heating rate is 35 DEG C/
Hour, 115 DEG C constant temperature 3 hours；
(4) it roasts：It after drying, is roasted 4 hours in muffle furnace in 450 DEG C, catalysis needed for being made after natural cooling
Agent；The total weight of active constituent oxide is the 50% of total catalyst weight in catalyst；Molybdenum oxide in active constituent oxide,
Nickel oxide, cobalt oxide, phosphate compounds weight ratio be 71：21：3.5：4.5.
(5) hydrocracking：By Catalyst packing into continuous fixed bed reactors, reforms ten tail oil of carbon and pass through fixed bed bed
Layer carries out pre-add hydrogen, hydrocracking and hydrofinishing with hydrogen under 385 DEG C, 9.0MPa Hydrogen Vapor Pressure and obtains hydrogenation products,
Middle hydrogen to oil volume ratio 2300, volume space velocity 1.0h-1；
(6) rectifying separates：Hydrogenation products obtained by step (5) are subjected to rectifying separation, wherein 135 DEG C of front-end volatiles accounting
12%, 135-145 DEG C of fraction accountings 4.5%, 150-180 DEG C of fraction accounting 7.5%, 178-215 DEG C of fraction accounting 10%, 210-
250 DEG C of fraction accountings 14.5%, 250 DEG C of tails accountings 51.5%；135 DEG C of front-end volatiles can be used as gasoline ready-mixed oil or into one
Isolated No. 6 solvent naphthas (60-90 DEG C of boiling range) and No. 90 solvent naphthas (90-120 DEG C) are walked, 135-145 DEG C of fraction is mixing two
Toluene, 150-180 DEG C of fraction are S1000 solvent naphtha, and 178-215 DEG C of fraction is S1500 solvent naphtha, 210-250 DEG C of fraction
For S2000 solvent naphtha；Distillation kettle liquid after 250 DEG C can be mixed with the heavy constituent tail oil of catalytic reforming C+10 heavy aromatic hydrocarbon,
Hydrocracking reaction is re-started, it is little on adding the oil property after hydrogen to influence.
Embodiment 2
(1) preparation of mixed solution：Take 18.39 grams of ammonium molybdate, 10.93 grams of nickel nitrate, 3.07 grams of cobalt nitrate and phosphoric acid
0.45 gram is dissolved in 51 milliliters of distilled water, forms mixed solution；
(2) it impregnates：32.25 grams of carriers of alumina silicate are gradually immersed in step (1) resulting mixed solution, are soaked at room temperature
Stain 10 hours；
(3) it dries：It takes out impregnated carrier to be put into drying box, rises to 105 DEG C from room temperature, heating rate is 40 DEG C/
Hour, 105 DEG C constant temperature 3 hours；
(4) it roasts：It after drying, is roasted 4 hours in muffle furnace in 500 DEG C, catalysis needed for being made after natural cooling
Agent；The total weight of active constituent oxide is the 35% of total catalyst weight in catalyst；Molybdenum oxide in active constituent oxide,
Nickel oxide, cobalt oxide, phosphate compounds weight ratio be 77：16：4.5：2.5.
(5) hydrocracking：By Catalyst packing into continuous fixed bed reactors, reforms ten tail oil of carbon and pass through fixed bed bed
Layer carries out pre-add hydrogen, hydrocracking and hydrofinishing with hydrogen under 370 DEG C, 6.5MPa Hydrogen Vapor Pressure and obtains hydrogenation products,
Middle hydrogen to oil volume ratio 1600, volume space velocity 1.6h-1；
(6) rectifying separates：Hydrogenation products obtained by step (5) are subjected to rectifying separation, wherein 135 DEG C of front-end volatiles accounting
10.5%, 135-145 DEG C of fraction accountings 7%, 150-180 DEG C of fraction accounting 9.5%, 178-215 DEG C of fraction accounting 13%, 210-
250 DEG C of fraction accountings 21%, 250 DEG C of tails accountings 39%；135 DEG C of front-end volatiles can be used as gasoline ready-mixed oil or further divide
From No. 6 solvent naphthas (60-90 DEG C of boiling range) and No. 90 solvent naphthas (90-120 DEG C) are obtained, 135-145 DEG C of fraction is mixed xylenes,
150-180 DEG C of fraction is S1000 solvent naphtha, and 178-215 DEG C of fraction is S1500 solvent naphtha, and 210-250 DEG C of fraction is
S2000 solvent naphtha；Distillation kettle liquid after 250 DEG C can be mixed with the heavy constituent tail oil of catalytic reforming C+10 heavy aromatic hydrocarbon, weight
It is new to carry out hydrocracking reaction, it is little on adding the oil property after hydrogen to influence.
Embodiment 3
(1) preparation of mixed solution：Take 13.79 grams of ammonium molybdate, 5.35 grams of nickel nitrate, 3.16 grams of cobalt nitrate and phosphoric acid 0.19
It gram is dissolved in 37 milliliters of distilled water, forms mixed solution；
(2) it impregnates：37.18 grams of carriers of alumina silicate are gradually immersed in step (1) resulting mixed solution, are soaked at room temperature
Stain 6 hours；
(3) it dries：It takes out impregnated carrier to be put into drying box, rises to 110 DEG C from room temperature, heating rate is 45 DEG C/
Hour, 110 DEG C constant temperature 3 hours；
(4) it roasts：It after drying, is roasted 4 hours in muffle furnace in 550 DEG C, catalysis needed for being made after natural cooling
Agent；The total weight of active constituent oxide is the 25% of total catalyst weight in catalyst；Molybdenum oxide in active constituent oxide,
Nickel oxide, cobalt oxide, phosphate compounds weight ratio be 81：11：6.5：1.5.
(5) hydrocracking：By Catalyst packing into continuous fixed bed reactors, reforms ten tail oil of carbon and pass through fixed bed bed
Layer carries out pre-add hydrogen, hydrocracking and hydrofinishing with hydrogen under 350 DEG C, 5MPa Hydrogen Vapor Pressure and obtains hydrogenation products, wherein
Hydrogen to oil volume ratio 950, volume space velocity 1.8h-1；
(6) rectifying separates：Hydrogenation products obtained by step (5) are subjected to rectifying separation, wherein 35 DEG C of front-end volatiles accounting
11%, 135~145 DEG C of fraction accountings 8.5%, 150-180 DEG C of fraction accounting 10.5%, 178-215 DEG C of fraction accounting 18%,
210-250 DEG C of fraction accounting 24%, 250 DEG C of tails accountings 28%；135 DEG C of front-end volatiles can be used as gasoline ready-mixed oil or into one
Isolated No. 6 solvent naphthas (60-90 DEG C of boiling range) and No. 90 solvent naphthas (90-120 DEG C) are walked, 135-145 DEG C of fraction is mixing two
Toluene, 150-180 DEG C of fraction are S1000 solvent naphtha, and 178-215 DEG C of fraction is S1500 solvent naphtha, 210-250 DEG C of fraction
For S2000 solvent naphtha；Distillation kettle liquid after 250 DEG C can be mixed with the heavy constituent tail oil of catalytic reforming C+10 heavy aromatic hydrocarbon,
Hydrocracking reaction is re-started, it is little on adding the oil property after hydrogen to influence.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is by appended claims and its is equal.
Claims (10)
1. a kind of ten tail oil catalyst for cracking of reformation carbon, which is characterized in that include the work of molybdenum, nickel, cobalt and phosphorus in the catalyst
Sexual element and silicic acid alumina supporter, the silicic acid alumina supporter account for the 25-50% of catalyst gross mass, and the active ingredient is by following
Mass percent group is grouped as：71-81% molybdenum oxide, 11-21% nickel oxide, 3.5-6.5% cobalt oxide and 1.5-4.5% phosphoric acid
Radical compound.
2. the preparation method described in claim 1 for reforming ten tail oil catalyst for cracking of carbon, which is characterized in that the preparation side
Method includes the following steps：
(1) preparation of mixed solution：It takes ammonium molybdate, nickel nitrate, cobalt nitrate and phosphoric acid to be dissolved in distilled water, forms mixed solution；
(2) it impregnates：Silicic acid alumina supporter is gradually immersed in mixed solution, is impregnated 6-10 hours at room temperature；
(3) it dries：It takes out impregnated carrier to be put into drying box, rises to 110 ± 5 DEG C from room temperature, heating rate is 40 ± 5
DEG C/h, 110 ± 5 DEG C constant temperature 3 hours；
(4) it roasts：It after drying, is roasted 4 hours in muffle furnace in 450-550 DEG C, catalysis needed for being made after natural cooling
Agent.
3. the preparation method according to claim 2 for reforming ten tail oil catalyst for cracking of carbon, which is characterized in that the silicon
Sour alumina supporter impregnates 4 times according to step (2) the method, and dipping front and back is dried according to step (3) the method every time.
4. the preparation method according to claim 2 for reforming ten tail oil catalyst for cracking of carbon, which is characterized in that step (1)
Described in ammonium molybdate, nickel nitrate, cobalt nitrate, phosphoric acid and distilled water mass ratio be 100：39-85:14-23:1.5-5:265-
275。
5. the preparation method according to claim 2 for reforming ten tail oil catalyst for cracking of carbon, which is characterized in that step (2)
Described in silicic acid alumina supporter and mixed solution mass ratio be 1:1.6-4.6.
6. ten tail oil catalyst for cracking of reformation carbon described in claim 1 is in reforming ten tail oil of carbon cracking production aromatic solvent
Using.
7. application according to claim 6, which is characterized in that the application concrete operation step is：
(a) hydrocracking：By Catalyst packing into continuous fixed bed reactors, reforms ten tail oil of carbon and passes through fixed bed bed,
Pre-add hydrogen, hydrocracking and hydrofinishing is carried out with hydrogen under 350-385 DEG C, 5.0-9.0MPa Hydrogen Vapor Pressure to obtain that hydrogen is added to produce
Object, the hydrogenation products contain benzene,toluene,xylene, trimethylbenzene, durene, penta-methyl benzene, non-aromatic light component and boiling point 220-
250 DEG C or more of tail oil；
(b) rectifying separates：Hydrogenation products obtained by step (a) are subjected to rectifying separation, 135 DEG C of front-end volatiles can be used as gasoline reconciliation
Oily or further isolated No. 6 solvent naphthas and No. 90 solvent naphthas, 135-145 DEG C of fraction is mixed xylenes, and 150-180 DEG C evaporates
It is divided into S1000 solvent naphtha, 178-215 DEG C of fraction is S1500 solvent naphtha, and 210-250 DEG C of fraction is S2000 solvent naphtha；
Distillation kettle liquid after 250 DEG C can be mixed with the heavy constituent tail oil of catalytic reforming C+10 heavy aromatic hydrocarbon, re-start hydrocracking
Reaction；No. 6 solvent naphtha boiling ranges are 60-90 DEG C, and the boiling range of No. 90 solvent naphthas is 90-120 DEG C；
It include the active ingredient and silicic acid alumina supporter of molybdenum, nickel, cobalt and phosphorus, the alumina silicate in catalyst described in step (a)
Carrier accounts for the 25-50% of catalyst gross mass, and the active ingredient is grouped as by following mass percent group：71-81% oxidation
Molybdenum, 11-21% nickel oxide, 3.5-6.5% cobalt oxide and 1.5-4.5% phosphate compounds.
8. application according to claim 7, which is characterized in that the volume space velocity for reforming ten tail oil of carbon is 0.6-2.5/
H, volume hydrogen-oil ratio are 600-2500：1.
9. application according to claim 7, which is characterized in that after the catalyst is packed into reactor, reformed being passed through
It is activated before ten tail oil of carbon, specific operating method is：Catalyst is fitted into continuous fixed bed reactors, it is straight to be passed through hydrogen
It is 3.0-4.0MPa to system pressure, establishes and recycle and gradually heat up 150 ± 5 DEG C, injects the sulphur containing carbon disulfide with high-pressure pump
Carburetion, and be gradually warming up to 320 ± 10 DEG C and vulcanized, vulcanization time is 28 hours, and the sulfurized oil is high boiling 1500#
Solvent naphtha, the quality of the carbon disulfide are 0.3 times of catalyst quality, and vulcanization oil quality is 30 times of catalyst quality.
10. application according to claim 9, which is characterized in that the air speed of the sulfurized oil containing carbon disulfide is
1.0/h, hydrogen-oil ratio 800:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710343287.1A CN108855163A (en) | 2017-05-16 | 2017-05-16 | A kind of ten tail oil catalyst for cracking of reformation carbon and its preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710343287.1A CN108855163A (en) | 2017-05-16 | 2017-05-16 | A kind of ten tail oil catalyst for cracking of reformation carbon and its preparation and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108855163A true CN108855163A (en) | 2018-11-23 |
Family
ID=64320725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710343287.1A Pending CN108855163A (en) | 2017-05-16 | 2017-05-16 | A kind of ten tail oil catalyst for cracking of reformation carbon and its preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108855163A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110372467A (en) * | 2019-08-05 | 2019-10-25 | 鹏辰新材料科技股份有限公司 | A method of the hydrocracking C10 aromartic based on extracting rectifying extracts durol |
| CN111286357A (en) * | 2020-02-14 | 2020-06-16 | 山东京博石油化工有限公司 | Production method of aromatic hydrocarbon solvent SA-1000 |
| CN115427539A (en) * | 2020-04-06 | 2022-12-02 | 托普索公司 | Selective production of light synthetic gasoline |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57212294A (en) * | 1981-06-25 | 1982-12-27 | Asahi Chem Ind Co Ltd | Pyrolysis of heavy hydrocarbon oil |
| CN101747935A (en) * | 2008-12-18 | 2010-06-23 | 中国石油化工股份有限公司 | Method for producing light olefins and monocyclic aromatic hydrocarbons from heavy hydrocarbons |
| CN102618321A (en) * | 2012-04-20 | 2012-08-01 | 江苏联东化工股份有限公司 | Method for synthesizing oil modifier by hydrogenating washing oil |
| CN104152179A (en) * | 2014-09-01 | 2014-11-19 | 江苏联东化工股份有限公司 | Production method of high-boiling-point aromatic solvent oil |
| CN104927917A (en) * | 2015-06-11 | 2015-09-23 | 江苏联东化工股份有限公司 | Method for producing high-boiling-point aromatic solvent oil through heavy benzol lightening |
| CN105176583A (en) * | 2015-10-12 | 2015-12-23 | 苏州常实工业设备有限公司 | Catalytic reforming preparation method of high performance solvent oil |
-
2017
- 2017-05-16 CN CN201710343287.1A patent/CN108855163A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57212294A (en) * | 1981-06-25 | 1982-12-27 | Asahi Chem Ind Co Ltd | Pyrolysis of heavy hydrocarbon oil |
| CN101747935A (en) * | 2008-12-18 | 2010-06-23 | 中国石油化工股份有限公司 | Method for producing light olefins and monocyclic aromatic hydrocarbons from heavy hydrocarbons |
| CN102618321A (en) * | 2012-04-20 | 2012-08-01 | 江苏联东化工股份有限公司 | Method for synthesizing oil modifier by hydrogenating washing oil |
| CN104152179A (en) * | 2014-09-01 | 2014-11-19 | 江苏联东化工股份有限公司 | Production method of high-boiling-point aromatic solvent oil |
| CN104927917A (en) * | 2015-06-11 | 2015-09-23 | 江苏联东化工股份有限公司 | Method for producing high-boiling-point aromatic solvent oil through heavy benzol lightening |
| CN105176583A (en) * | 2015-10-12 | 2015-12-23 | 苏州常实工业设备有限公司 | Catalytic reforming preparation method of high performance solvent oil |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110372467A (en) * | 2019-08-05 | 2019-10-25 | 鹏辰新材料科技股份有限公司 | A method of the hydrocracking C10 aromartic based on extracting rectifying extracts durol |
| CN110372467B (en) * | 2019-08-05 | 2022-03-15 | 鹏辰新材料科技股份有限公司 | Method for extracting durene by hydrocracking of deca-aromatic hydrocarbons based on extractive distillation |
| CN111286357A (en) * | 2020-02-14 | 2020-06-16 | 山东京博石油化工有限公司 | Production method of aromatic hydrocarbon solvent SA-1000 |
| CN111286357B (en) * | 2020-02-14 | 2022-03-15 | 山东京博石油化工有限公司 | Production method of aromatic hydrocarbon solvent SA-1000 |
| CN115427539A (en) * | 2020-04-06 | 2022-12-02 | 托普索公司 | Selective production of light synthetic gasoline |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102992932B (en) | Method for removing olefin in aromatic hydrocarbon by M-SBA-15 type mesoporous molecular sieve | |
| CN103464193B (en) | Fluidized catalyst for alcohol ether and hydrocarbon aromatization, and preparation method and application method thereof | |
| CN108855163A (en) | A kind of ten tail oil catalyst for cracking of reformation carbon and its preparation and application | |
| CN103131456B (en) | A kind of method of being synthesized liquefied petroleum gas (LPG) and BTX aromatics by butanols | |
| CN107185594B (en) | Preparation method of Ni-Zn-K-Ru/MOF catalyst | |
| CN102992931A (en) | Method for synthesizing light aromatic hydrocarbon and liquefied petroleum gas from low carbon number oxygen-containing compound mixed raw material | |
| CN107999100B (en) | Light alkane aromatization catalyst and preparation method and application thereof | |
| CN102029157A (en) | Catalyst used for coal tar pitch hydrocracking lightening reaction | |
| CN104557423A (en) | Method for preparing arene by directly converting methane | |
| CN102310006A (en) | Method for regenerating and pre-vulcanizing hydrogenation catalyst | |
| CN110694673A (en) | Aromatization catalyst of waste edible oil and preparation method and application thereof | |
| CN101302439A (en) | Hydrocatalyst for preparing fuel by hydrodealkylation of coal-tar pitch and preparation thereof | |
| CN111871448B (en) | Catalyst for improving oxygen-free aromatization reaction performance of methane and preparation method thereof | |
| CN104689846A (en) | Catalyst for adjusting product components in process of preparing arene from oxygen-containing compound and application of catalyst | |
| CN106554821B (en) | The method that aromatic hydrocarbons and porous charcoal/solid acid rich in dimethylbenzene are prepared from bio oil | |
| CN102614909B (en) | Hydrodenitrogenation catalyst capable of removing nitrogen-containing compound from coal tar, and preparation method and application thereof | |
| CN108906098A (en) | A kind of mesoporous TiO 2 cladding catalyst of phosphatizing nickel constitutes the preparation method of core-shell structure catalyst | |
| CN109569719B (en) | Carbon-based catalyst for light alkane aromatization and preparation method thereof | |
| CN107213913A (en) | A kind of preparation method of low-carbon alkanes producing light olefins catalyst | |
| CN103816928A (en) | Hydrofining catalyst, and preparation method and application thereof | |
| CN108246341A (en) | The preparation method and application method of a kind of hydrogenation dearomatization catalyst | |
| CN107603668B (en) | Method for producing light aromatic hydrocarbon by acetylene trimerization | |
| CN102863308B (en) | Method for preparing olefin by catalyzing and cracking naphtha | |
| CN101229516A (en) | Catalyst for removing organic chloride contained in hydrocarbon and preparing method thereof | |
| CN111054447A (en) | Catalyst capable of purifying and condensing catalytic cracking of coal tar and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181123 |
|
| RJ01 | Rejection of invention patent application after publication |