CN104475146B - Catalytic cracking gasoline alkylation desulphurization catalyst and preparation method thereof - Google Patents
Catalytic cracking gasoline alkylation desulphurization catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention provides a catalytic cracking gasoline alkylation desulphurization catalyst and a preparation method thereof. The catalyst is characterized in that the catalyst is prepared through processing an HY molecular sieve, active alumina and a transition metal oxide, the HY molecular sieve accounts for 50-90% of the weight of the catalyst, and the transition metal oxide accounts for 0.1-1.0% of the weight of the catalyst, wherein the Si/Al molar ratio of the HY molecular sieve is 8-16, the aperture of the catalyst is 4-15nm, and the specific surface area of the catalyst is 400-1200m＜2＞/g. The catalyst has a good alkylation desulphurization performance, and allows above 93% of sulfur-containing organic compounds in the catalytic cracking gasoline to be converted by adopting a fixed bed simulation reactor at a temperature of 50-150DEG C under a pressure of 0.5-1.5MPa under a raw material volume space velocity of 1.0-5.0h＜-1＞.
Description
Technical field
The present invention relates to catalysis technical field, specially a kind of catalytic gasoline alkylation desulfurization catalyst and its system
Method.More particularly, it relates to one kind low boiling organic compounds containing sulfur and alkene can occur alkylated reaction in catalytic gasoline
Catalyst and preparation method thereof.
Technical background
At present, account for more than the 80% of national gasoline composition in Chinese catalytically cracked gasoline, in catalytically cracked gasoline, contain 1 ‰
～2 ‰ compound state sulphur, the SO generating after the burning of these organic compounds containing sulfursX, not only pollute environment, and serious harm people
Class is healthy；The organic compounds containing sulfur therefore reducing and removing in catalytically cracked gasoline is must step.Simultaneously with people
Continuous concern to environmental protection, the requirement standard more and more higher to sulfur content in gasoline, the national requirements sulphur such as current European Union
In below 10 μ g/g, the U.S. requires gasoline content in below 30 μ g/g to content, Japan require sulfur content in gasoline 10 μ g/g with
Under, and China requires sulfur content in gasoline in below 50 μ g/g, Beijing has required sulfur content in gasoline in 10 μ g/ by contrast
Below g, and will carry out in the whole nation to this standard in 2018.Because domestic crude oil supply and demand still can not be self-sufficient, import according to
Degree of depositing is still very big, and crude oil sulfur content constantly raises, and sweet crude is in short supply, therefore it is required that developing and improving gasoline desulfurization skill
Art.
Gasoline desulfurization technology can be divided into hydrodesulfurization and non-hydrodesulfurization.Gasoline desulfurization at this stage relies primarily on hydrodesulfurization
Technology, this technology while organic compounds containing sulfur, also can cause octane number to reduce in removing catalytically cracked gasoline, and
And invest and operating cost height.Non-hydrodesulfurization includes abstraction desulfurization, biological desulphurization, oxidation sweetening and alkylating desulfurization etc.
Deng.Wherein alkylating desulfurization technology has that operating condition is simple, desulfurized effect is good, the low advantage of expense, by increasing
Concern；And the continuous development with sieve technology, alkylating desulfurization will become the important way of deep desulfurization of gasoline.
Alkylating desulfurization technology is proposed by BP company earliest.This technology utilize catalytically cracked gasoline in olefine selective with
There is alkylated reaction in thiophene-based organic compounds containing sulfur (main organic compounds containing sulfur composition in catalytically cracked gasoline), raw
Become the bigger alkylthrophene of molecular mass.These alkylthrophene elevations of boiling point, by distillation by higher boiling alkylthrophene from bottom of towe
Extraction, sulfur-free gasoline obtains sulfur-free gasoline product from overhead extraction.This technology not only completes industrial experiment at present, and in moral
Beyer Co., Ltd of state has been put into application.Although this technology has good economic benefit；But this technology is institute of BP company
Have, domestic there is no maturation and examples of industrial application, the development of alkylation techniques, alkylating and desulfurizing catalyst and technique skill in addition
The improvement of art, new alkylating and desulfurizing catalyst and technique need to be further improved, and therefore develop new alkylation desulfurization and urge
Agent and its process matched therewith have significant significance of times and economic benefit.
CN 100460486 discloses a kind of alkylating desulfurization method, and the method is with the ion exchange of carried metal halide
Resin, as catalyst, imports in reactor using full distillation gasoline is preheated, the heavy constituent alkane of generation after alkylated reaction afterwards
Base sulfide is through distillation removing.The method proposes multiple reactor parallel arrangement, using low-carbon (LC) organic solvent, deactivator is carried out
Regeneration is processed, and reaches the continuous purpose run of alkylated reaction.But this invention is difficult to meet Deep Desulfurization of FCC Gasoline
Require.
CN 101264452B discloses a kind of catalyst and its preparation removing sulfide in petrol by alkylated reaction
Method, the method passes through halogens to the modification of high silica alumina ratio Y molecular sieve, by infusion process, halogens is loaded to shaping point
On son sieve, then dry roasting and obtain catalyst.The method compared for the alkylation effect of two kinds of halogens of F, Cl, and the method uses
The analog gasoline being made up of thiophene, hexene, dimethylbenzene and hexahydrotoluene, result demonstrates thiophene alkylation effect and pays no attention to
Think.
CN 101875849A discloses a kind of gasoline alkylation desulfuration method, and the method adopts solid phosphoric acid catalyst, adopts
It is prepared from infusion process, the Siliceous MCM-41 mesopore molecular sieve that catalyst carrier synthesizes for hydro-thermal method, dipping solution is burnt phosphorus
Sour and ortho-phosphoric mixed solution.Using batch reactor, react before and after's thiophene situation of change by gas chromatography analysis, right
Compare the alkylation effect of fresh catalyst cracking gasoline and analog gasoline.But this invention converts to thiophene-based in catalytically cracked gasoline
Rate only has 75%, is 80% to thiophene-based conversion ratio in analog gasoline, is difficult to reach the industrial requirements of deep desulfuration.
CN 101543787B discloses a kind of preparation side of the MCM-22 molecular sieve catalyst for alkylation desulfurization of gasoline
Method, the Na type MCM-22 molecular sieve removing template is placed in aqueous slkali, stir 1～10h, be washed out to neutrality, after use nitre
Acid ammonium solution exchanges, and is dried, and roasting is obtained H type MCM-22 molecular sieve catalyst.Using simulation fixed bed reactors, using by thiophene
Fen, hexene, dimethylbenzene, the analog gasoline of hexahydrotoluene composition, alkylate uses gas chromatography analysis product to form
Situation of change.Result shows using the MCM-22 catalyst of 0.5mol/L, 0.5h alkali process, the thiophene of analog gasoline is had very
Good alkylation activity.But raw material high cost in the method, complicated process of preparation.
Content of the invention
It is an object of the invention to provide the catalytic gasoline alkylation desulfurization catalyst of a kind of high activity, high stability
And preparation method thereof.
The invention provides the catalytic gasoline alkylation desulfurization catalyst of high-effect high stability, by splitting to catalysis
The alkylated reaction experiment changing gasoline draws：Its alkylating desulfurization rate is more than 93% it is achieved that good desulfurized effect.
The present invention is a kind of catalytic gasoline alkylation desulfurization catalyst and its preparation method.
Present invention firstly relates to a kind of catalytic gasoline alkylation desulfurization catalyst, by HY molecular sieve, activated alumina
And transition metal oxide composition it is characterised in that：
1) molecular sieve used by is SiO2/Al2O3HY molecular sieve between 8～16 for the mol ratio, molecular sieve butt accounts for catalyst
The 50%～90% of gross mass；
2) mass content of transition metal oxide is 0.1%～1.0%；
3) remaining material is activated alumina；
4) catalyst aperture is between 4nm～15nm；Specific surface area is in 400m2/ g～1200m2Between/g；
Described catalyst, Na in HY molecular sieve2The mass content of O be less than 1%, described transition metal oxide be ZnO or
NiO.
The invention still further relates to a kind of preparation method of catalytic gasoline alkylation desulfurization catalyst it is characterised in that：
1) HY molecular sieve, activated alumina and transition metal salt are mixed according to aforementioned proportion；
2) step 1) described in transition metal salt be selected from as ZnCl2、Zn(NO3)2、ZnSO4、NiCl2、Ni(NO3)2Or
NiSO4, the mass content being added ZnO or NiO of metering is the 0.1%～1.0% of catalyst gross mass, pinches after mixing
Close extruded moulding, dry at 100 DEG C～130 DEG C, roasting 3～8h at 450 DEG C～650 DEG C, make alkylating and desulfurizing catalyst.
According to catalyst of the present invention and preparation method, further relate to described made catalyst and be alkylated in catalytically cracked gasoline
Purposes in desulfurization and usage；It is characterized in that；
Described catalyst needed to use inert gas high-temperature activation before being reacted, and activation condition is 350～500
DEG C, pressure is 0.1～1.0MPa, and inert gas flow velocity is 0.1～1.0L/h-1, inert gas is N2, one of He, Ar；
Described catalyst in catalytically cracked gasoline alkylating desulfurization usage, including：Fresh catalytically cracked gasoline is led
Enter in reactor, be 50～150 DEG C in temperature, pressure is 0.5～1.0MPa, during liquid, volume space velocity is 1.0～5.0h-1Descend and urge
Agent contact occur alkylated reaction, product collects after cooling, is fractionated using distilling apparatus, 180 DEG C with
Front composition is light distillate, as sulfur-free gasoline, and after 180 DEG C, composition is heavy distillate, then utilizes Agilent7890B gas
Chromatography carries out component analysis, the composition of component and changes of contents before and after contrast reaction.
Zn or Ni that the present invention achieves HY molecular sieve first is metal-modified, the acidity sieved by metal-modified Molecular regulator
Position and acid amount, change the ratio of L acid and B acid so as to reach a kind of optimal acid strength and acid amount purpose.Test result indicate that changing
Catalyst after property has significant alkylating desulfurization effect to catalytically cracked gasoline.
It is an advantage of the current invention that：Catalysis can be split by the modified HY zeolite alkylating and desulfurizing catalyst of present invention preparation
Change organic compounds containing sulfur in gasoline and be converted into higher boiling organic sulfur compound, show very high alkylation activity and stability,
Alkylating desulfurization rate is more than 93%.
Specific embodiment
Catalytic gasoline alkylation desulfurization catalyst provided by the present invention, goes for fixed bed reactors, shifting
All kinds of reactors such as dynamic bed reactor, simulation moving bed reactor.Embodiment is given below, but does not limit it because of embodiment
Range.
Embodiment 1
Take SiO2/Al2O3Mol ratio is 20 HY molecular sieve 160g, activated alumina 40g, mixes, is subsequently adding
Zn (the NO of 0.734g3)2·6H2O extruded moulding, after 150 DEG C dry, roasting 6h at 500 DEG C, it is obtained containing 0.1wt%ZnO's
Catalyst A.Using the 20mL simulation fixed bed reactors for 11mm for the internal diameter, load this catalysis of 20～40 purposes in reactor
Agent, catalyst is using front through N2400 DEG C of purging activation 4h, gas speed for 200mL/min and then is naturally cooling to 100 DEG C, then uses N2
Fresh catalyst cracking gasoline press-in reactor, to 0.5MPa, is reacted after the completion of boosting by lifting reacting system pressure with pump,
After reaction, oil product intercepts 180 DEG C of following components as sulfur-free gasoline by the use of simulation distilling apparatus, using gas chromatographic analysis desulfurization
Content of sulfur in gasoline changes.
Embodiment 2
Take SiO2/Al2O3Mol ratio is 20 HY molecular sieve 160g, activated alumina 40g, mixes, is subsequently adding
Zn (the NO of 3.685g3)2·6H2O extruded moulding, after 150 DEG C dry, roasting 6h at 500 DEG C, it is obtained containing 0.5wt%ZnO's
Catalyst B.Reaction evaluating process is with embodiment 1.
Embodiment 3
Take SiO2/Al2O3Mol ratio is 20 HY molecular sieve 160g, activated alumina 40g, mixes, is subsequently adding
Zn (the NO of 7.407g3)2·6H2O extruded moulding, after 150 DEG C dry, roasting 6h at 500 DEG C, it is obtained containing 1.0wt%ZnO's
Catalyst C.Reaction evaluating process is with embodiment 1.
Comparative example 1
Take SiO2/Al2O3Mol ratio is 20 HY molecular sieve 160g, activated alumina 40g, mixed-forming, 150 DEG C of drying
Afterwards, roasting 6h at 500 DEG C, prepared catalyst D.Reaction evaluating process is with embodiment 1.
Embodiment 4
Take SiO2/Al2O3Mol ratio is 20 HY molecular sieve 160g, activated alumina 40g, mixes, is subsequently adding
Ni (the NO of 0.779g3)2·6H2O extruded moulding, after 150 DEG C dry, roasting 6h at 500 DEG C, it is obtained containing 0.1wt%NiO's
Catalyst E.Reaction evaluating process is with embodiment 1.
Reaction condition and the results are shown in Table 1
The alkylation activity to gasoline for the metal-modified HY molecular sieve catalyst of table 1
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Embodiment 4 |
| Catalyst | Catalyst A | Catalyst B | Catalyst C | Catalyst D | Catalyst E |
| Reaction temperature (DEG C) | 100 | 100 | 100 | 100 | 100 |
| Reaction pressure (MPa) | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Volume space velocity (h-1) | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| Reaction time (h) | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 |
| Yield of gasoline (%) | 95 | 94 | 95 | 84 | 95 |
| Desulfurization degree (%) | 94 | 96 | 93 | 78 | 90 |
Can be seen that in the catalyst of the present invention by above-described embodiment and comparative example result, HY molecular sieve is through transition metal
Zn modified hence it is evident that improve the alkylation activity of catalyst, can effectively remove sulfur-bearing in catalytically cracked gasoline and organise
Compound.
Claims (3)
1. a kind of catalytic gasoline alkylation desulfurization catalyst it is characterised in that：By HY molecular sieve, activated alumina and transition
Metal oxide forms；
（1）Molecular sieve used is SiO2/Al2O3Mol ratio is 8 ~ 16 HY molecular sieve, and molecular sieve butt accounts for catalyst gross mass
50%~90%；
（2）The mass content of transition metal oxide is 0.1% ~ 1.0%；
（3）Remaining material is activated alumina；
（4）Described catalyst aperture is 4nm ~ 15nm；Specific surface area is 400m2/g~1200m2/g；
Described catalyst, Na in HY molecular sieve2The mass content of O is less than 1%, described transition metal oxide be ZnO or
NiO.
2. the catalytic gasoline alkylation desulfurization catalyst described in a kind of claim 1 preparation method it is characterised in that：
（1）HY molecular sieve, activated alumina and transition metal salt are mixed according to the ratio of claim 1；
（2）Step（1）Described in transition metal salt be selected from as ZnCl2、Zn(NO3)2、ZnSO4、NiCl2、Ni(NO3)2Or
NiSO4, the mass content being added ZnO or NiO of metering is the 0.1% ~ 1.0% of catalyst gross mass, mediates after mixing
Extruded moulding, dries at 100 DEG C ~ 130 DEG C, roasting 3 ~ 8h at 450 DEG C ~ 650 DEG C, makes alkylating and desulfurizing catalyst.
3. according to purposes on catalytically cracked gasoline alkylating desulfurization for the catalyst described in claim 1 it is characterised in that：
Described catalyst needed to use inert gas high-temperature activation before being reacted, and activation temperature is 350 ~ 500 DEG C, activation
Pressure is 0.1 ~ 1.0MPa, and inert gas flow velocity is 0.1 ~ 1.0L/h-1, inert gas is N2, one of He, Ar；Will be fresh
Catalytically cracked gasoline import reactor in, temperature be 50 ~ 150 DEG C, pressure be 0.5 ~ 1.0MPa, during liquid, volume space velocity is
1.0~5.0h-1Lower and after activation catalyst contacts generation alkylated reaction, and product collects after cooling, using steaming
Distillation unit is fractionated, and 180 DEG C of former compositions are light distillate, and 180 DEG C of later compositions are heavy distillate, then utilize
Agilent7890B gas chromatograph carries out component analysis, the composition of component and changes of contents before and after contrast reaction.
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| CN101264452B (en) * | 2007-03-14 | 2010-09-15 | 中国科学院大连化学物理研究所 | Catalyst for removing sulfide in gasoline by alkylation reaction and preparation thereof |
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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant after: CHINA NATIONAL OFFSHORE OIL Corp. Applicant after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Applicant after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant before: CHINA NATIONAL OFFSHORE OIL Corp. Applicant before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Applicant before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |
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