CN107754846A - The reformate olefin-reducing catalyst for aromatic hydrocarbons of long-term operation - Google Patents
The reformate olefin-reducing catalyst for aromatic hydrocarbons of long-term operation Download PDFInfo
- Publication number
- CN107754846A CN107754846A CN201610710680.5A CN201610710680A CN107754846A CN 107754846 A CN107754846 A CN 107754846A CN 201610710680 A CN201610710680 A CN 201610710680A CN 107754846 A CN107754846 A CN 107754846A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- aromatic hydrocarbons
- long
- olefin
- reformate
- 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
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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- 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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/16—Metal oxides
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a kind of reformate olefin-reducing catalyst for aromatic hydrocarbons of long-term operation, mainly solves the problem of current techniques are existing to cause catalyst inactivation very fast because activated centre matches bad with Reaction-diffusion terms, and service life is short.The olefin-reducing catalyst for aromatic hydrocarbons of the long-term operation of the present invention, in terms of catalyst weight percent, including following component：0.01~15% lanthanide series or its mixture；The oxide of 0.01~8% one or more of elements in Na, K, Mg, Ca, Sr, Ba；0.01~10% is one or more of selected from Ga, Sn, In, Ge, Bi element；The technical scheme of 40~90% Y type molecular sieve, preferably solve the problem, it is active good, the advantages of long lifespan, it can be used in the industrial production of aromatic hydrocarbons Olefin decrease.
Description
Technical field
The invention belongs to a kind of reformate olefin-reducing catalyst for aromatic hydrocarbons.
Background of invention
The present invention relates to a kind of reformate olefin-reducing catalyst for aromatic hydrocarbons, specifically improves the catalyst service life.
Aromatic hydrocarbons is the base stock of petrochemical industry, and it mostlys come from Aromatic Hydrocarbon United Plant.After catalytic reforming reaction
Reformate aromatic hydrocarbon product contain a certain amount of olefin impurity.Alkene chemistry property is active, and not only easily polymerization forms colloid,
But also easily reacted with other components, undesirable components are generated, so as to be produced to the quality and plant running of aromatic hydrocarbon product
Considerable influence.
Aromatic hydrocarbons subsequent production technique such as dimethylbenzene adsorption separation process is to alkene caused by reformate or other drippolenes
It is especially sensitive, even if the content of olefin impurity is a small amount of, can also very detrimental effect be produced to technical process.It is qualified in order to obtain
Subsequent production needed for industrial chemicals and ensure the stable operation of subsequent technique, have removing trace amounts of olefin impurity unit.
Due to refining step all in most Aromatic Hydrocarbon United Plants using carclazyte as refining agent, as low pressure is reformed
Popularization, gum level increase in reformate, the puzzlement that carclazyte is brought will be more serious, substitute the efficient deolefination of industrial carclazyte
Catalyst and application technology are into trend.
Clay-filtered is to contact aroamtic hydrocarbon raw material with atlapulgite, reaches de- using the suction-operated and catalytic action of carclazyte
Except the purpose of olefin impurity.Carclazyte has acid centre, under the conditions of high pressure liquid phase, 150~200 DEG C, has certain catalysis
Overlapping ability and duct adsorption capacity, the trace amounts of olefin that can make to contain in reformate occur the reaction such as hydrocarbonylation, polymerization, generate height boiling
Point compound, then by bleaching earth adsorption, or is removed in later separation flow.Typical catalyst CN102091648A,
It is described in the patents such as CN1232862, CN102658196A, and is cited in full text herein.Although carclazyte has removing alkene
Ability, but because its specific surface area is smaller, pore structure is undeveloped, therefore inactivate very fast, the life-span is shorter, and due to inactivation after
Carclazyte high temperature regeneration pore structure is obviously reduced, and causes deolefination ability to decline larger, and regenerability is poor, causes carclazyte frequent more
Change, and the carclazyte after inactivation can only cause environmental pollution by buried processing.
It is another to there is deolefination technique to remove alkene under the conditions of using noble metal hydrogenation.Hydrofinishing route exist hydrogen circulation and
The separation problem of hydrogen and oil product is, it is necessary to set up the equipment such as compressor, gas-liquid separator and stripper, and technique is complex, energy
Consumption is high, and used catalyst is mostly noble metal catalyst, expensive.
Hydrofinishing is using noble metal platinum or palladium catalyst after petroleum reforming technique, aroamtic hydrocarbon raw material is carried out " rear to add
Hydrogen process ", make alkene saturation and remove olefin impurity, typical catalyst CN85100760A, CN85100215A,
In the patents such as CN1448474A, CN101260320A.But come for the wide component of aromatic hydrocarbons simultaneously containing benzene, toluene and dimethylbenzene
To say, hydrogenation reaction depth is difficult to take into account comprehensively, and the aromatic hydrocarbons such as low boiling toluene are formed after C9 aromatic and the hydrogenation of the above when special,
Make the loss of aromatic hydrocarbon product larger.
Molecular sieve is the artificial synthesized alumionsilicate crystalline body with spacious multidimensional structure.Compared with carclazyte, molecular sieve
Specific surface area is high, has higher appearance charcoal ability, lasts a long time；The acidity of molecular sieve is the unsaturated coordination production by skeletal atom
Raw, therefore acidity is basically unchanged after high temperature regeneration, reproducibility is preferable, thus molecular sieve catalyst have preferable stability and compared with
The long life-span.In view of the above-mentioned advantage of molecular sieve catalyst, it has been disclosed that many achievements in research and using molecular sieve as key component
The olefinic hydrocarbon expelling catalyzer of preparation.It is active component and 20% aluminum oxide that EP0895977A1, which is disclosed based on 80% molecular sieve,
Extrusion is mediated by binding agent of acid Alusil, the particle that 20-40 mesh is ground into after drying and roasting is finished catalyst.WO 01/
It is that active component and clay carrier shaping prepare catalyst removal alkene to be described in 30942A1 using mesoporous molecular sieve MCM-22
Hydrocarbon, the extrusion rate of alkene are higher than 95%.CN1618932A, CN 103495435A are described under conditions of non-hydrogen, using molecular sieve
For active component, aluminum oxide or kaolin are the method that carrier prepares catalyst, and catalyst has renewable recycling.
It is main active component that one kind is described in CN102008976A by high silica alumina ratio ReUSY molecular sieves, with mordenite molecular sieve
For the second active component, aluminum oxide is binder component, adds inorganic acid or organic acid carries out kneading extrusion, drying roasting obtains
Catalyst.But in above-mentioned invention disclosed patent, the acidity of its catalyst is mainly supplied by molecular sieve, and this is for weight
It is whole oil in trace amounts of olefin by alkylated reaction remove for be weaker, higher reaction temperature ability is needed during use
Reach the purpose for thoroughly removing alkene, do not only result in energy consumption increase, also result in coking carbon distribution, the reaction of aromatic hydrocarbons dealkylation, aromatic hydrocarbons
The generation of the side reactions such as cracking, causes the loss of aromatic hydrocarbons.
Chinese patent CN1618932 describes one kind catalytic refining reforming aromatic oil catalyst under conditions of non-hydrogen.Should
Catalyst is non-loading type solid acid catalyst, using the catalyst treatment reforming aromatic oil, in 100~300 DEG C of reaction temperature,
0.5~3.0MPa of reaction pressure, during air speed 0.5~40-1Under the conditions of, the trace amounts of olefin in energy Arene removal, but although this is urged
Agent can regenerate reuse, but its single pass life is still too short, when air speed is 15-1Under the conditions of check and rate 18 hours after,
Its activity is just reduced to 50%, thus commercial Application is very limited.
The problem of the invention aims to overcome the conventional catalyst for removing olefins from reforming oil life-span low, because molecular sieve is general
It is difficult to the life for reaching catalyst all over using transition metal modified acid regulation, a kind of modification of element, multiple element is difficult
To form more effective modified effect, therefore the problem of the life-span can not form better effects.
The content of the invention
The present invention relates to reformate aromatic hydrocarbons olefinic hydrocarbon expelling catalyzer, mainly solve the conventional catalyst for removing olefins from reforming oil life-span compared with
The problem of low.By effective ways when molecular sieve is modified, major element is by molecular sieve modified after addition, preferably
Solves problem, catalyst has the advantages of long lifespan.
The present invention uses a kind of reformate olefin-reducing catalyst for aromatic hydrocarbons of long-term operation, with catalyst weight percent
Meter, including following component：
A) one or more of mixtures in 0.01~15% lanthanide series；
B) oxide of 0.01~8% one or more of elements in Na, K, Mg, Ca, Sr, Ba；
C) 0.01~10% is one or more of selected from Ga, Sn, In, Ge, Bi element；
D) 40~90% Y type molecular sieve；
E) selected from aluminum oxide, the one or more of silica.
For in above-mentioned offer technical scheme：
Y molecular sieve is that have to adjust pore passage structure and acidity in a big way, as chain carrier supplier and carrier,
It is 40~90% that its content, which accounts for catalyst, accounting for by weight percentage for optimization, contains 50~85% Y type molecular sieve.Typically
Industrial production is NaY, can either subsequent treatment obtains HY or USY molecular sieve by ion exchange.Therefore catalyst molecule
Sieve the one or more for NaY, HY, USY.Various molecular sieves are modified to obtain by hydro-thermal process, soda acid processing method
In above-mentioned technical proposal, containing one or more of mixtures in 0.01~15% lanthanide series, optimization contains 0.3
~10% lanthanide series or its mixture.
In above-mentioned technical proposal, one or more of selected from Ga, Sn, In, Ge, Bi element containing 0.5~5%, optimization contains
0.5~3% after the one or more in Na, K, Mg, Ca, Sr, Ba major element oxide.Described element is being molded
Before, shaping in, shaping after simultaneously or it is different when in introduce.
In above-mentioned technical proposal, salic in catalyst and silica.
Molecular sieve after silica or alumina binder shaping and roasting with obtaining the molecular sieve catalyst containing a certain amount of pore volume.
Silica or account for 10~60% or so of weight with aluminum oxide in the catalyst.Preferable scope silica or and aluminum oxide
Account for overall catalyst weight 12~40%.
Catalyst is prepared according to the technical program, the described reformate Olefin decrease reaction condition that is used for is in temperature 130~260
DEG C, 0.3~5.0MPa of pressure, 0.1~10h of weight space velocity-1。
In aromatic hydrocarbons catalyst for removing olefins from reforming oil, employ rear major element and be modified and adjust catalyst, typically
It is adjusted using transition elements and alkaline element, so as to obtain preferable catalyst, but due to above transition elements and alkalescence
Element, which be combined with each other, to be not easy, and causes catalyst active center to be matched not enough with reaction.The present invention passes through rear major element, Ke Yiyu
Lanthanide series and alkaline element interaction, reach preferable activity, catalyst active center is had preferable reactivity worth
And uniformity, so as to reduce the generation of side reaction, so as to extend the life-span of catalyst.Catalyst prepared by the invention passes through coordination
Modified and reaction matching method, solves the problems, such as that the life-span of conventional catalyst is shorter.
By using example below, the invention will be further elaborated：
Embodiment
【Embodiment 1】
Containing 3.0wt%LaO, 1.0wt%Na2O USY (SiO2/Al2O3Than 7.0), and 25.0wt% aluminum oxide
Catalyst 60.0g, using SnSO4Solution (containing Sn3.0wt%) 38g incipient impregnations, after dry 550 DEG C are calcined 3 hours, use
Mg(NO3)2Solution (1.0wt% containing Mg) 35g incipient impregnations, dry 520 DEG C of roastings and obtain catalyst A in 3.0 hours.
3.0g catalyst is taken to carry out the experiment of reformate non-hydrogen deolefination in fixed bed reactors, raw material is reformation
Oil, bromine index are 1200 milligrams of Br/100 grams of oil (reaction raw materials evaluation that all examples below uses).Activity calculates public
Formula is as follows：
Reaction pressure：2.0MPa, temperature：160 DEG C, air speed：When 10.0-1, Activity Results 2 hours 95%, 100 hours
90.5%, 200 hours 82.0%.
【Embodiment 2】
Containing 2.0wt%LaO and 2.0wt%CeO2, 0.5wt%Na2O USY (SiO2/Al2O3Than 12.0), and
The catalyst 60.0g of 25.0wt% aluminum oxide, using Ga (NO3)3Solution (1.5wt% containing Ga) 40g incipient impregnations, dry
After 500 DEG C are calcined 4 hours, using Ca (NO3)2Solution (0.5wt% containing Ca) 36g incipient impregnations, dry 550 DEG C of roastings 2.5
Hour obtains catalyst B.
3.0g catalyst is taken to carry out the experiment of reformate non-hydrogen deolefination, reaction pressure in fixed bed reactors：
5.0MPa, temperature：180 DEG C, air speed：8.0 when-1, Activity Results 2 hours 95.0%, 100 hours 88.0%, 200 hours
80.1%.
【Embodiment 3】
Containing 2.0wt%LaO and 2.0wt%CeO2, 0.5wt%Na2O USY (SiO2/Al2O3Than 12.0), and
The catalyst 60.0g of 10.0wt% aluminum oxide, using Ga (NO3)3Solution (1.5wt% containing Ga) 40g incipient impregnations, dry
After 500 DEG C are calcined 4 hours, using Ca (NO3)2Solution (0.5wt% containing Ca) 36g incipient impregnations, dry 600 DEG C of roastings 2.0
Hour obtains catalyst C.
3.0g catalyst is taken to carry out the experiment of reformate non-hydrogen deolefination, reaction pressure in fixed bed reactors：
3.0MPa, temperature：170 DEG C, air speed：5.0 when-1, Activity Results 2 hours 96.0%, 100 hours 92.0.0%, 200 hours
89.0%.
【Embodiment 4】
Containing 0.01wt%LaO, 0.3wt%Na2O USY (SiO2/Al2O3Than 12.0), and 35.0wt% aluminum oxide
Catalyst 60.0g, using Ga (NO3)3Solution (1.5wt% containing Ga) 40g incipient impregnations, dry 500 DEG C and be calcined 4 hours
Afterwards, using Ca (NO3)2Solution (0.5wt% containing Ca) 36g incipient impregnations, dry 550 DEG C of roastings and obtain catalyst in 3.0 hours.
3.0g catalyst is taken to carry out the experiment of reformate non-hydrogen deolefination, reaction pressure in fixed bed reactors：
3.0MPa, temperature：260 DEG C, air speed：8.0 when-1, as a result 2 hours 96.0%, 100 hours 95.0%, 200 hours 91.0%.
【Embodiment 5】
Containing 0.01wt%LaO, 0.01wt%Na2O USY (SiO2/Al2O3Than 12.0), and 25.0wt% aluminum oxide
Catalyst 60.0g, using Bi (NO3)3Solution (5.0wt% containing Bi) 40g incipient impregnations, dry 500 DEG C and be calcined 4 hours
Afterwards, using Sr (NO3)2Solution (0.01wt% containing Sr) 36g incipient impregnations, dry 600 DEG C of roastings and be catalyzed for 1.5 hours
Agent.
3.0g catalyst is taken to carry out the experiment of reformate non-hydrogen deolefination, reaction pressure in fixed bed reactors：
1.0MPa, temperature：130 DEG C, air speed：5.0 when-1, as a result 2 hours 96.0%, 100 hours 91.0%, 200 hours 86.5%.
【Embodiment 6】
Containing 1.6wt%Na2O USY (SiO2/Al2O3Than 5.0), 0.9wt%GeO and 25.0wt% aluminum oxide are urged
Agent 60.0g, using being handled 3 hours at 500g90 DEG C of 1M acetic acid solutions, after drying 500 DEG C of roastings 4 hours, using containing K (NO3)2
Solution (0.3wt% containing K) and containing Sn (NO3)2Solution (2.0wt% containing Sn) 200g impregnates, and filters 500 DEG C of roastings and obtains for 3 hours
Catalyst.
3.0g catalyst is taken to carry out the experiment of reformate non-hydrogen deolefination, reaction pressure in fixed bed reactors：
0.3MPa, temperature：130 DEG C, air speed：3.0 when-1, Activity Results 2 hours 98.0%, 100 hours 97.0%, 200 hours
92.8%.
【Embodiment 7】
Containing 0.2wt%Na2O USY (SiO2/Al2O3Than 18.0), 15.0wt%LaO and 45.0wt% aluminum oxide
Catalyst 60.0g, using being handled 3 hours at 90 DEG C of 0.3M sulfuric acid solutions 500g, after drying after 600 DEG C of roastings 4 hours, use
Sn(NO3)2Solution (8.0wt% containing Sn) 200g impregnates, and filters 700 DEG C of roastings and obtains catalyst in 1 hour.
3.0g catalyst is taken to carry out the experiment of reformate non-hydrogen deolefination, reaction pressure in fixed bed reactors：
2.0MPa, temperature：170 DEG C, air speed：2.0 when-1, as a result 2 hours 95.0%, 100 hours 94.5%, 200 hours 93.8%.
【Embodiment 8】
Containing 0.5wt%Na2O HY (SiO2/Al2O3Than 4.5), 8.0wt%BaO and 20.0wt% silica
Catalyst 60.0g, using being handled 2 hours at 90 DEG C of 0.2M citric acid solutions 300g, after drying after 450 DEG C of roastings 4 hours, adopt
With Sb (NO3)2Solution (2.0wt% containing Sb) 150g impregnates, and filters 550 DEG C of roastings and obtains catalyst in 2 hours.
3.0g catalyst is taken to carry out the experiment of reformate non-hydrogen deolefination, reaction pressure in fixed bed reactors：
3.0MPa, temperature：170 DEG C, air speed：1.0 when-1, as a result 2 hours 93.0%, 200 hours 91.8%.
【Embodiment 9】
Containing 1.2wt%Na2O NaHY (SiO2/Al2O3Than 5.0), 10wt%GaO and 15.0wt% silica and
The catalyst 60.0g of 5% aluminum oxide, after lower 600 DEG C of water vapours (moisture vapor 0.08MPa) processing processing of normal pressure 2 hours,
Using containing Sn (NO3)2Solution (2.0wt% containing Sn) and containing Bi (NO3)3Solution (6.0wt% containing Bi) 150g impregnates, filtering 550
DEG C roasting obtains catalyst in 2 hours.
3.0g catalyst is taken to carry out the experiment of reformate non-hydrogen deolefination, reaction pressure in fixed bed reactors：
2.0MPa, temperature：170 DEG C, air speed：2.0 when-1, Activity Results 2 hours 96.8.0%, 100 hours 95.8%, 200 hours
95.0%.
【Embodiment 10】
Containing 0.3wt%Na2O USY (SiO2/Al2O3Than 11.0), the catalyst of 1.0wt%CaO and 15% aluminum oxide
60.0g, after lower 700 DEG C of water vapours (moisture vapor 0.05MPa) processing processing of normal pressure 1 hour, using Sn (NO3)2Solution
(3.2wt% containing Sn) 190g impregnates, and filters 550 DEG C of roastings and obtains catalyst in 2 hours.
3.0g catalyst is taken to carry out the experiment of reformate non-hydrogen deolefination, reaction pressure in fixed bed reactors：
3.0MPa, temperature：170 DEG C, air speed：When 0.1-1, as a result 2 hours 98.50%, 200 hours 98.4%.
3.0g catalyst is taken to carry out the experiment of reformate non-hydrogen deolefination, reaction pressure in fixed bed reactors：
5.0MPa, temperature：260 DEG C, air speed：6.0 when-1, as a result 2 hours 98.00%, 200 hours 94.4%.
【Embodiment 11】
Containing 0.8wt%Na2O USY (SiO2/Al2O3Than 10.0), the catalyst of 1.9wt%CeO and 15% aluminum oxide
60.0g, using Sn (NO3)2Solution (3.2wt% containing Sn) 190g impregnates, and filters 550 DEG C of roastings and obtains catalyst in 2 hours.
3.0g catalyst is taken to carry out the experiment of reformate non-hydrogen deolefination, reaction pressure in fixed bed reactors：
3.0MPa, temperature：170 DEG C, air speed：2.0-1, as a result 2 hours 96.50%, 200 hours 95.4%.
Claims (10)
1. a kind of reformate olefin-reducing catalyst for aromatic hydrocarbons of long-term operation, in terms of catalyst weight percent, including it is following several
Individual component：
A) one or more of mixtures in 0.01~15% lanthanide series；
B) oxide of 0.01~8% one or more of elements in Na, K, Mg, Ca, Sr, Ba；
C) 0.01~10% is one or more of selected from Ga, Sn, In, Ge, Bi, Sb element；
D) 40~90% Y type molecular sieve；
E) 10~60% selected from aluminum oxide, the one or more of silica.
2. the reformate olefin-reducing catalyst for aromatic hydrocarbons of long-term operation according to claim 1, it is characterised in that with weight hundred
Divide than meter, containing one or more of mixtures in 0.3~10% lanthanide series.
3. the reformate olefin-reducing catalyst for aromatic hydrocarbons of long-term operation according to claim 1, it is characterised in that with weight hundred
Divide than meter, the oxide of one or more of elements containing 0.5~3% in Na, K, Mg, Ca, Sr, Ba.
4. the reformate olefin-reducing catalyst for aromatic hydrocarbons of long-term operation according to claim 1, it is characterised in that with weight hundred
Divide than meter, select Ga, Sn, In, Ge, Bi element one or more of containing 0.5~5%.
5. the reformate olefin-reducing catalyst for aromatic hydrocarbons agent of long-term operation according to claim 1, it is characterised in that with weight
Percentages, contain 50~85% Y type molecular sieve.
6. the reformate olefin-reducing catalyst for aromatic hydrocarbons of long-term operation according to claim 1, it is characterised in that described Y types point
Son sieve is NaY, HY, USY one or more.
7. the reformate olefin-reducing catalyst for aromatic hydrocarbons of long-term operation according to claim 1, it is characterised in that Y molecular sieve leads to
Hydro-thermal process, ion exchange, soda acid processing method is crossed to be modified.
8. the reformate olefin-reducing catalyst for aromatic hydrocarbons of long-term operation according to claim 1, it is characterised in that described group
Element in point a), b) and c) before the forming, in shaping, after shaping simultaneously or it is different when in introduce.
9. the reformate olefin-reducing catalyst for aromatic hydrocarbons of long-term operation according to claim 1, it is characterised in that in catalyst
Salic and silica.
10. a kind of method of the reformate aromatic hydrocarbons Olefin decrease of long-term operation, it is catalyzed using any one in claim 1~9
Agent, it is characterised in that the described reformate Olefin decrease that is used for is in 130~260 DEG C, 0.3~5.0MPa of pressure of temperature, weight space velocity 0.1
~10h-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610710680.5A CN107754846B (en) | 2016-08-23 | 2016-08-23 | The reformate olefin-reducing catalyst for aromatic hydrocarbons of long-term operation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610710680.5A CN107754846B (en) | 2016-08-23 | 2016-08-23 | The reformate olefin-reducing catalyst for aromatic hydrocarbons of long-term operation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107754846A true CN107754846A (en) | 2018-03-06 |
| CN107754846B CN107754846B (en) | 2019-11-08 |
Family
ID=61264794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610710680.5A Active CN107754846B (en) | 2016-08-23 | 2016-08-23 | The reformate olefin-reducing catalyst for aromatic hydrocarbons of long-term operation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107754846B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112657535A (en) * | 2019-10-16 | 2021-04-16 | 中国石油化工股份有限公司 | Olefin removal catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070144939A1 (en) * | 2005-12-28 | 2007-06-28 | Chevron U.S.A. Inc. | Hydrocarbon conversion using molecular sieve ssz-74 |
| CN104549472A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Aromatic alkyl transferring and deolefination catalyst and application thereof |
| CN105080592A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | Aromatic olefin-reducing catalyst and use thereof |
-
2016
- 2016-08-23 CN CN201610710680.5A patent/CN107754846B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070144939A1 (en) * | 2005-12-28 | 2007-06-28 | Chevron U.S.A. Inc. | Hydrocarbon conversion using molecular sieve ssz-74 |
| CN104549472A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Aromatic alkyl transferring and deolefination catalyst and application thereof |
| CN105080592A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | Aromatic olefin-reducing catalyst and use thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112657535A (en) * | 2019-10-16 | 2021-04-16 | 中国石油化工股份有限公司 | Olefin removal catalyst and preparation method and application thereof |
| CN112657535B (en) * | 2019-10-16 | 2023-01-24 | 中国石油化工股份有限公司 | Olefin removal catalyst, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107754846B (en) | 2019-11-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107754845A (en) | High life reformate olefine lowering catalyst | |
| CN1217892C (en) | Process for producing aromatic hydrocarbon compounds and liquefied petroleum gas from hydrocarbon feedstock | |
| CN101434508B (en) | Selective hydrogenation method for alkyne | |
| CN101935544B (en) | Method for processing catalytically cracked gasoline | |
| KR101896733B1 (en) | Method for producing single-ring aromatic hydrocarbons | |
| CN101347748B (en) | Regeneration method of aluminum compensation for molecular sieve | |
| CN101370755B (en) | Process for production of propylene and aromatic hydrocarbon, and apparatus for the process | |
| CN105080592A (en) | Aromatic olefin-reducing catalyst and use thereof | |
| CN101428235B (en) | Regeneration method of molecular sieve catalysts | |
| CN103121906A (en) | Method for preparing mononuclear aromatics by using polycyclic aromatic hydrocarbon | |
| CN105618082A (en) | Selective hydrogenation catalyst for reformate, preparation method and application | |
| CN101993320B (en) | Aromatization method for producing light aromatics | |
| CN101596461A (en) | A kind of aromatizing catalyst for light hydrocarbon and preparation method thereof | |
| CN103509601B (en) | Technological process for co-production of propane by aromatization of carbon tetrad-hydrocarbon | |
| CN103495435B (en) | A kind of catalyst for removing olefins from reforming oil and preparation method thereof | |
| CN102078819A (en) | Light hydrocarbon aromatization catalyst and preparation method thereof | |
| CN102233274B (en) | Catalyst for reducing alkene content in aromatic hydrocarbon, and a preparation method thereof | |
| CN106925339A (en) | Preparation method of hierarchical pore molecular sieve catalyst for xylene isomerization reaction in carbon octaarene | |
| CN101081997B (en) | Catalytically cracked gasoline non-hydrogen aromatization modified catalyst and preparation method thereof | |
| CN1317467A (en) | Process for processing low-carbon paraffin | |
| CN107754846B (en) | The reformate olefin-reducing catalyst for aromatic hydrocarbons of long-term operation | |
| CN108940354A (en) | A kind of C10+Heavy aromatics selective hydrogenation ring opening catalyst and preparation method thereof | |
| CN1191331C (en) | Dual-function reforming catalyst containing Pt and Sn and its preparing process | |
| CN102069008B (en) | Catalyst for removing olefin in reformed arene and preparation method thereof | |
| CN112657540A (en) | Toluene disproportionation and transalkylation catalyst, and preparation method 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |