CN1094968C - Gasoline fraction hydrogenating and modifying catalyst containing zeolite - Google Patents
Gasoline fraction hydrogenating and modifying catalyst containing zeolite Download PDFInfo
- Publication number
- CN1094968C CN1094968C CN99122230A CN99122230A CN1094968C CN 1094968 C CN1094968 C CN 1094968C CN 99122230 A CN99122230 A CN 99122230A CN 99122230 A CN99122230 A CN 99122230A CN 1094968 C CN1094968 C CN 1094968C
- Authority
- CN
- China
- Prior art keywords
- zeolite
- content
- catalyzer
- heavy
- nickel
- 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.)
- Expired - Lifetime
Links
Abstract
The present invention relates to a gasoline fraction hydrogenating and modifying catalyst containing zeolite, which comprises molybdenum and/or tungsten, nickel and/or cobalt, assistant magnesium, one or several kinds of zeolite with large holes or middle holes, and an aluminum oxide substrate. On a basis of the oxide and by taking the total weight of the catalyst as a reference, the content of the molybdenum and/or the tungsten is from 3 to 20 wt%, the content of the nickel and the cobalt is from 0.3 to 2 wt%, the content of the assistant magnesium is from 1 to 7 wt%, and the content of the zeolite is from 5 to 60 wt%. The assistant magnesium exists in the catalyst in the form of the oxide. The catalyst can not obviously reduce the octane value and liquid yield of gasoline while the sulfur in a gasoline fraction is eliminated.
Description
The invention relates to a kind of catalyzer that is used for the gasoline fraction hydro-upgrading.Specifically, the invention relates to a kind of zeolite that contains, be used for the gasoline fraction hydro-upgrading, to remove the catalyzer of the sulphur in the gasoline.
As everyone knows, atmospheric pollution brings serious environmental problem.A large amount of engine exhaust emissions is to cause the air-polluting major cause.In recent years, for adapting to the protection environment requirement, countries in the world have proposed stricter restriction to the composition of motor spirit, in the hope of reducing emission of harmful substances.The combustionmaterial SOx of sulfide in petrol mainly contains one of harmful substances, and it also is one of essential substance of poisoning auto-exhaust catalyst simultaneously.U.S.'s clean air amendment requires sulfur in gasoline content to be lower than the mean level (ML) of nineteen ninety 339ppm.And, required sulfur in gasoline content to be lower than 40ppm in 1996 at California, USA.Japan's specification gasoline in 1996 requires sulphur content to be not more than 100ppm; The EN228 white gasoline standard-required sulphur content that European Union formulates is not more than 500ppm, and other developed country is also just taking similar measure.Therefore the further desulfurization of gasoline has become a problem of current oil Refining Technologies.
Meanwhile, China need from the about 5,000 ten thousand tons crude oil of external import to estimate by 2000, and wherein major part is a middle-eastern crude, and sulphur content is higher.According to present catalytic cracking technology, adopt the catalytically cracked material of sulphur content about 1%, the gained sulfur content of catalytic cracking gasoline will reach 1000-1500ppm.
In China, catalytically cracked gasoline accounts for about 70% of gasoline formation, and the sulphur content that how to reduce in the catalytically cracked gasoline is very important and urgent to total sulfur content in the reduction gasoline.
Contain relatively large alkene in the gasoline fraction, particularly catalytically cracked gasoline, thereby, higher octane value had.Traditional Hydrobon catalyst, as the Hydrobon catalyst that contains nickel, cobalt metal oxide or the sulfide of the group vib metal that loads on silicon oxide, aluminum oxide or the silica-alumina carrier and group VIII can remove the sulphur in the gasoline fraction, but, because the lower alkene of collateralization degree very easily hydrogenation is saturated to low-octane alkane, so adopt traditional Hydrobon catalyst, in desulfurization, must follow the rapid decline of gasoline octane rating.Hydrodesulfurization reaction and hydrogenation of olefins saturated reaction are shown in equation (1) and (2).
In equation (1), sulfide R
1SR
2Can be thio-alcohol (R at this moment,
1Be alkyl, R
2Be H), thioether class (R at this moment,
1, R
2Be alkyl, S and R
1, R
2In the C atom link to each other) and thiophene-based (R at this moment,
1And R
2Link to each other by heterocycle).
Equation (2) is not wish the hydrogenation of olefins saturated reaction that takes place in the gasoline hydrodesulfurizationmethod reaction.This reaction consumes hydrogen, catalyzed alkene generates low-octane saturated alkane, causes the octane value of hydrogenation after product sharply to descend.
Given this, in the prior art, when adopting traditional Hydrobon catalyst to remove sulphur in the gasoline fraction, have to adopt and earlier gasoline fraction is divided into weight two portions, after the part of counterweight is carried out hydrogenating desulfurization, the light part that to tell is again carried out the blended method with the part of the weight of process hydrogenating desulfurization, obviously, and this method too complex.
For example, US3,957,625 mainly are enriched in the characteristics of catalytically cracked gasoline last running according to sulfide, invented a kind of method that reduces sulphur content in the catalytically cracked gasoline product, this method comprises that (1) heats up in a steamer gasoline fraction in 180～300 punishment of cut point becomes high boiling part and lower boiling part, and described high boiling part contains high-load sulphur, and described lower boiling part is rich in alkene; (2) high boiling part is contacted with a kind of desulfurization catalyst, described desulfurization catalyst is a kind of cobalt-molybdenum-aluminum oxide desulfurization catalyst, this catalyzer also contains a kind of auxiliary agent, described auxiliary agent is selected from one group that is made up of barium, magnesium, calcium and rare earth, described catalytic temperature, pressure and air speed can effectively be carried out desulfurization, and reduce the content of alkene in the desulfurization product indistinctively; (3) lower boiling that (2) desulfurization product that obtains of step and (1) step are obtained and the product that is rich in alkene mix, and obtain a kind of sulphur content minimizing and have high-octane sweet gasoline.
US4,062,762 discloses a kind of sulfur method of petroleum naphtha, and this method comprises that (1) is divided at least a more lower boiling cut, a kind of cut of middle boiling point and a kind of cut of higher with petroleum naphtha; (2) cut with boiling point in the middle of described contacts with a kind of basic metal, and this cut is carried out desulfurization; (3) cut with described higher contacts with a kind of Hydrobon catalyst with hydrogen, and this cut is carried out desulfurization; (4) desulfurization product in recovery (2) and (3) step; And (5) product that (4) step was obtained mixes with described more lower boiling cut, obtains the petroleum naphtha of low sulfur content.
US5,266,188 disclose a kind of selective hydrodesulfurization method of hydrotreated feed, this method is included in 300～700 of temperature of reaction, under the existence of reaction pressure 50～600psig and a kind of catalyzer, with described charging and H-H reaction, described catalyzer contains a kind of hydrogenation component and a kind of carrier component, described hydrogenation component comprises a kind of group vib metal component and a kind of VIII family metal component, in oxide compound, and with the total catalyst weight is benchmark, and the content of described group vib metal component is 4～20 heavy %, and the content of VIII family metal component is 0.5～10 heavy %; Described carrier component contains the magnesium component of 0.5～50 heavy % and the alkaline components of 0.02～10 heavy %.
In recent years, many catalyst for hydro-upgrading that contain zeolite have been developed.
US3,759,821 disclose a kind of method for modifying of catalytically cracked gasoline, and this method comprises described catalytically cracked gasoline is fractionated into a kind of C
6Below and C
7Above cut is with described C
7Above cut contacts with ZSM-5 or ZSM-8 zeolite, and with the product and the C that obtain
6Following cut mixes the gasoline that obtains a kind of octane value raising.Wherein, can use with a kind of porous matrix as the ZSM-5 or the ZSM-8 zeolite of catalyzer, zeolite content therein is 1～95 heavy %, preferred 50～80 heavy %.Described matrix comprises metal and alloy, agglomerating metal, agglomerating glass, asbestos, silicon carbide aggregation, foam, refractory brick, diatomite and inorganic oxide.Inorganic oxide such as clay, chemically treated clay, silicon oxide, silica-alumina are preferred.Can also contain hydrogenation component in the described zeolite, these hydrogenation component comprise simple substance, oxide compound and the sulfide of group vib metal, IIB family metal, VIII family metal.
US5,503,734 disclose a kind of method for modifying of sulfur-bearing catalytic cracking cut, the boiling point of 95% in the described catalytic cracking cut is at least 325 and its boiling spread in the gasoline boiling spread, this method is included in first reaction zone, under high temperature, high pressure and nitrogen atmosphere, described catalytic cracking cut is contacted with a kind of Hydrobon catalyst, obtain a kind of intermediate product, this intermediate product contains to compare with raw material and has than low sulfur content and more low-octane liquid distillate; And, at second reaction zone, in the presence of hydrogen, the part of the boiling point in the described at least intermediate product in the gasoline boiling spread contacted with a kind of catalyst system, make heavy paraffin hydrocarbon be cracked into light alkane and make to have low-octane normal paraffin in the intermediate product and change into high-octane product.Catalyzer in described first reaction zone is conventional hydrotreating catalyst, and the catalyst system in described second reaction zone has acid function, and it contains a kind of mesopore zeolite and large pore zeolite with hydrogenating function.
US5,865,988 disclose the sulfur-bearing of a kind of boiling range in gasoline-range and the method for modifying of the raw material of alkene, this method is included in the first step, comprising that temperature is under 400-800 the mild hydrocracking condition, the sulfur-bearing raw material is contacted with a kind of solid acid catalyst, be aromatic hydrocarbons and side chain aromatic hydrocarbons with the conversion of olefines in the raw material, and make low-octane alkane and cracking of olefins in the raw material, form a kind of intermediate product; Under high temperature, high pressure and hydrogeneous atmosphere, the intermediate product that obtains is contacted with a kind of Hydrobon catalyst, make the sulfocompound in the intermediate product change into inorganic sulfide compound, and obtain a kind of C
6-C
10Aromaticity content is less than 50% desulfurization product.Solid acid catalyst wherein is a kind of shape slective cracking catalyzer, the shape slective cracking catalyzer that particularly contains the mesopore Si-Al zeolite, described mesopore Si-Al zeolite can be ZSM-5, ZSM-11, ZSM-12, ZSM-21, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, MCM-22, MCM49, MCM56, MCVM-36 etc.
US5,685,972 disclose and a kind of raw material are being carried out upgrading, when producing Fuel Petroleum, and the method for producing benzene,toluene,xylene from the cracking sulfur-bearing naphtha fraction of boiling point in the gasoline fraction scope, this method comprises, at first reaction zone, under high temperature, high pressure and nitrogen atmosphere, described charging is contacted with a kind of Hydrobon catalyst, obtain a kind of intermediate product, this intermediate product contains to compare with raw material and has than low sulfur content and more low-octane liquid distillate; And, at second reaction zone, the part of boiling point in the described intermediate product in the gasoline boiling spread contacted with a kind of catalyzer with acid function, make it change into a kind of effluent that contains gasoline fraction, this gasoline fraction has the octane value higher than the gasoline fraction in the intermediate product; From described effluent, extract by product benzene, toluene and C
8Following aromatic hydrocarbons and a kind of gasoline product.Wherein, described catalyzer with acid function is the catalyzer that contains mesopore zeolites such as ZSM-5, ZSM-11, ZSM-12, ZSM-21, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, MCM-22, contain restricted index and reach 2 large pore zeolite, also can use as the catalyzer of mordenite, Beta zeolite, faujusite.Can contain the hydrogenation component molybdenum in the catalyzer.
US5,275,720 disclose a kind of method for hydrogen cracking of hydrocarbon raw material, this method is included under 450-850 the temperature, under the pressure of 750-3500psig (5.1-23.8 MPa), reaching ammonia content in the presence of hydrogen is not higher than in the atmosphere of 200ppm, described hydrocarbon raw material is contacted with a kind of catalyzer, described catalyzer contains hydrogenation component, the sealumination modified Y zeolite that the heavy % of Beta zeolite and 15-50 has catalytic activity, the lattice constant of described Y zeolite is the 24.40-24.63 dust, is under the condition of 4.6 mmhg at 25 ℃ with steam partial pressure, and the water vapor adsorption capacity of this zeolite is at least 20 heavy %, and the silica alumina ratio of this zeolite is at least 6.US5,160,033 also disclose a kind of similar hydrocracking catalyst.
US4,618,594 disclose a kind of hydrodenitrification and hydrocracking catalyst that is used for the high nitrogen-containing raw material, this catalyzer contains a kind of hydrogenation component, a kind of crystalline zeolite molecular sieve and a kind of inorganic oxide, described hydrogenation component contains chromium, molybdenum, tungsten and at least a VIII family metal, and described zeolite molecular sieve is selected from ZSM series zeolite and AMS series molecular sieve, and described hydrogenation component exists with the form of simple substance, oxide compound, sulfide or their mixtures.
In the prior art, overcome traditional Hydrobon catalyst in, the shortcoming that gasoline octane rating reduces significantly to the gasoline fraction hydrogenating desulfurization though contain the catalyzer of molecular sieve.But, adopt this catalyzer that contains molecular sieve, to the gasoline fraction hydrogenating desulfurization the time, all be accompanied by the intensive cracking reaction, the reactant gases product is increased, cause liquid yield to reduce significantly.
The purpose of this invention is to provide a kind of newly, when reducing content of sulfur in gasoline, significantly do not reduce the gasoline fraction hydrogenating and modifying catalyst that contains zeolite of gasoline octane rating and liquid yield.
Catalyzer provided by the invention contains one or more and the alumina host in molybdenum and/or tungsten, nickel and/or cobalt, auxiliary agent magnesium, macropore and the mesopore zeolite; In oxide compound and with the total catalyst weight is benchmark, and the content of described molybdenum and/or tungsten is that the content of 3～20 heavy %, nickel and/or cobalt is that 0.3～2 heavy %, auxiliary agent Mg content are 1～7 heavy %, and the content of described zeolite is 5～60 heavy %.
According to catalyzer provided by the invention, described auxiliary agent magnesium is present in the catalyzer with the form of oxide compound.
According to catalyzer provided by the invention, under the preferable case, this catalyzer contains one or more and the alumina host in tungsten, nickel and cobalt, auxiliary agent magnesium, macropore and the mesopore zeolite; In oxide compound and with the total catalyst weight is benchmark, the content of tungsten is preferably 4～15 heavy %, the content of nickel and cobalt is preferably 0.5～1.5 heavy %, wherein, the atomic ratio of nickel and cobalt is 5～80, be preferably 10～30, the content of magnesium is preferably 1～5 heavy %, and the content of described zeolite is preferably 10～35 heavy %.
Described macropore and mesopore zeolite comprise existing various macropore and mesopore zeolite, as being in faujusite, mordenite, ZSM-5 zeolite, Beta zeolite, the omega zeolite one or more.In y-type zeolite, ZSM-5 and the mordenite that preferred zeolite is Hydrogen or rare-earth type one or more.More preferred zeolite is that the y-type zeolite of Hydrogen or rare-earth type, particularly lattice constant are the Hydrogen of 24.55～24.75 dusts or the y-type zeolite of rare-earth type.
Auxiliary agent magnesium, molybdenum and/or tungsten in the described catalyzer and nickel and/or cobalt can load on the mixture that contains zeolite and aluminum oxide, also can only load on the aluminum oxide, under latter event, zeolite can be used as a kind of component and is dispersed in the catalyzer, also can have an independent existence with the form of aluminum oxide and zeolite mixture.
Catalyzer of the present invention can adopt following method preparation:
(1) with hydrated aluminum oxide and molecular sieve mixing moulding, drying, 500～700 ℃ of roastings 1～6 hour under air again, makes the aluminum oxide that contains molecular sieve.
(2) aqueous solution of magnesium-containing compound, molybdenum and/or tungsten compound, nickel and/or the cobalt compound that immersion prepares in containing the aluminum oxide of molecular sieve, drying promptly obtained catalyst prod in 2～5 hours 350～500 ℃ of following roastings.
Wherein, auxiliary agent magnesium can immerse simultaneously with main active ingredient molybdenum and/or tungsten and nickel and/or cobalt, also can immerse prior to main active ingredient.
Auxiliary agent magnesium and main active ingredient molybdenum and/or tungsten and nickel and/or cobalt also can adopt on the aluminum oxide after above-mentioned pickling process directly loads on the moulding that does not contain molecular sieve, mix with the aluminum oxide that contains molecular sieve after dry, the roasting again and are prepared into catalyzer.
The compound water solution of described auxiliary agent magnesium, molybdenum, tungsten, nickel and cobalt can prepare according to a conventional method.The compound of magnesium, molybdenum, tungsten, nickel and cobalt is selected from one or more in their soluble compound respectively.Wherein one or both in the preferred magnesium nitrate of the compound of magnesium, the magnesium chloride, more preferably magnesium nitrate.The preferred ammonium molybdate of the compound of molybdenum.In the preferred ammonium tungstate of the compound of tungsten, ammonium metawolframate, ethyl ammonium metawolframate, the metatungstic acid nickel one or more.The compound of nickel and cobalt is preferably one or more in nickelous nitrate, Xiao Suangu, nickelous chloride, cobalt chloride, basic nickel carbonate, the cobaltous dihydroxycarbonate respectively.
Described hydrated aluminum oxide comprises one or more in unformed aluminium hydroxide, false boehmite, pseudo-boehmite, gibbsite, the surge aluminium stone, is preferably a false diaspore or pseudo-boehmite.
Described forming method can be existing various forming method, the method for preferred extruded moulding.
Catalyzer provided by the invention is applicable to the hydro-upgrading process of the gasoline fraction of sulfur-bearing, can significantly not reduce the octane value and the liquid yield of gasoline in removing gasoline fraction in the sulphur.Wherein, described gasoline fraction can be various gasoline fractions, as being catalytically cracked gasoline, coker gasoline, straight-run spirit, pressure gasoline etc.Wherein, because the sulphur content in catalytically cracked gasoline and the coker gasoline is higher, need remove especially, therefore, the gasoline fraction of described sulfur-bearing is preferably catalytically cracked gasoline or coker gasoline.
Catalyzer provided by the invention is when the hydro-upgrading process of the gasoline fraction that is used for sulfur-bearing, and the processing condition that are suitable for are the processing condition of gasoline hydrogenation modifying routine, and for example, temperature of reaction is 200～400 ℃, is preferably 250～350 ℃; The hydrogen dividing potential drop is 0.8～6 MPa, is preferably 1～4 MPa; Liquid hourly space velocity is 1～15 hour
-1, be preferably 2～8 hours
-1Hydrogen to oil volume ratio is 50～800, is preferably 100～500.
Catalyzer provided by the invention can carry out prevulcanized with existing pre-curing technology before use, makes hydrogenation metal become sulphided state, also can not carry out prevulcanized, directly uses the catalyzer of oxidation state.
Catalyzer provided by the invention has following advantage:
1. catalyzer provided by the invention has higher aromizing ability, lower lytic activity, and in hydrogenating desulfurization, the aromatic hydrocarbons that makes conversion of olefines become to have higher octane equally.Therefore, when it had both overcome the employing hydrotreating catalyst, alkene was by saturated in a large number, generate low octane rating alkane, the shortcoming that the gasoline fraction octane value is reduced has significantly overcome again simultaneously and has adopted when having zeolite containing catalyst now, cracking reaction is serious, causes liquid to receive the shortcoming that reduces significantly.Adopt method provided by the invention, in hydrogenating desulfurization, can keep less anti-knock index loss of product gasoline and higher liquid to receive.
For example, adopting catalyzer provided by the invention is 39-184 ℃ to a kind of boiling range, olefin(e) centent 25.98 body %, and the catalytically cracked gasoline of total sulfur content 1470ppm carries out hydro-upgrading, 330 ℃ of temperature of reaction, reaction pressure 3.2 MPas, liquid hourly space velocity 4 hours
-1, under the condition of hydrogen to oil volume ratio 150, reaching at desulfurization degree under the condition of 99.7 heavy %, the anti-knock index loss has only 1.25 units, and it is 97.3 heavy % that liquid is received.And under similarity condition, adopt when having zeolite containing catalyst now, though desulfurization level is close,, its liquid is received has only 91.2 heavy %.And when adopting existing hydrotreating catalyst, its anti-knock index bust 9 units.
2. catalyzer provided by the invention need not to be the saturated catalyst hydrogenation activity that on purpose reduces of minimizing alkene, thereby the catalyst hydrogenation constituent element keeps active condition, can reach higher desulfurization level.
3. catalyzer provided by the invention is applicable to one section conventional hydrogenation modifying process to full cut high-sulfur gasoline fraction, thereby, adaptability to raw material is strong, adopt catalyzer provided by the invention, can will not be fractionated into different boiling range scopes by gasoline fraction only with one section reaction, can reduce operation steps, simultaneously, reduce facility investment.
The following examples will the invention will be further described.
Example 1
This example illustrates Preparation of catalysts provided by the invention.
(1) get 30 parts of (weight, down with) Rare Earth Y (REY) zeolites (lattice constant is 24.60 dusts, and rare earth oxide content is 12.0 heavy %, wherein, La
2O
3Account for 73.8 heavy % of total amount of the rare earth oxide, CeO
2Account for 25.2 heavy % of total amount of the rare earth oxide, other rare earth oxides account for 1.0 heavy % of total amount of the rare earth oxide), 70 parts of (dry basis, down together) pseudo-boehmites (solid content is 69%, and Shandong Aluminum Plant produces), 3 parts of sesbania powder mix.Nitric acid and water that to take by weighing 4 parts of citric acids and 3.2 parts of concentration be 67 heavy % are made into 60 parts of solution.This solution under agitation is added in the mixed powder, pinches through mixing, extrusion, make diameter and be 1.6 millimeters trilobal cross bar.Extrudate was descended dry 4 hours at 120 ℃,, make the carrier that contains zeolite again in 600 ℃ of roastings 4 hours.
(2) take by weighing Xiao Suangu 0.12 gram, nickelous nitrate 2.73 grams, (concentration is 73.99 gram WO to measure ammonium metatungstate solution
3/ 100 milliliters) 8.1 milliliters, 15.3 milliliters of magnesium nitrate solutions (concentration be 50 gram magnesium nitrate/100 milliliter) are made into 34.3 milliliters of co-impregnated solutions with water.The carrier that contains zeolite that is made by (1) step with this solution impregnation 48.3 grams 4 hours, then 120 ℃ of dryings 4 hours, 500 ℃ of roastings 4 hours make catalyzer C provided by the invention
1Catalyzer C
1In nickel, cobalt, tungsten, magnesium oxide content and zeolite content as shown in table 1, in the table 1 in each catalyzer the part of less than 100% be aluminum oxide, still, in table, do not list the content of aluminum oxide.Each component concentration is got by calculating.
Comparative Examples 1 (DB1)
The preparation of this Comparative Examples explanation reference catalyst.
Take by weighing Xiao Suangu 0.24 gram, nickelous nitrate 5.46 grams, (concentration is 73.99 gram WO to measure ammonium metatungstate solution
3/ 100 milliliters) 16.2 milliliters, magnesium nitrate solution (concentration 50 gram magnesium nitrate/100 milliliter) is made into 57.5 milliliters of co-impregnated solutions with water for 30.6 milliliters.With this solution impregnation 96.6 gram content of magnesia is the gama-alumina (Chang Ling refinery catalyst plant product) 4 hours of 2 heavy %, and then 120 ℃ of dryings 4 hours, 500 ℃ of roastings 4 hours make reference catalyst B
1Reference catalyst B
1In nickel, cobalt, tungsten, magnesium oxide content as shown in table 1.
Comparative Examples 2 (DB2)
The preparation of this Comparative Examples explanation reference catalyst.
(1) prepares the carrier that contains zeolite by example 1 described method.
(2) take by weighing Xiao Suangu 0.124 gram, nickelous nitrate 2.82 grams are measured ammonium metatungstate solution (concentration 73.99 gram WO
3/ 100 milliliters) 8.4 milliliters, be made into 34.3 milliliters of co-impregnated solutions with water.The carrier that contains zeolite that is made by (1) step with this solution impregnation 48.3 grams 4 hours, then 120 ℃ of dryings 4 hours, 500 ℃ of roastings 4 hours make reference catalyst B
2Catalyst B
2Middle nickel, cobalt, tungsten oxide content and zeolite content are as shown in table 1.
Example 2
This example illustrates Preparation of catalysts provided by the invention.
(1) get 30 parts of Hydrogen Y (HY) zeolite (lattice constant is 24.60 dusts), 210 parts of pseudo-boehmites (with example 1), 9 parts of sesbania powder mix.Nitric acid and water that to measure 10 parts of concentration be 67 heavy % are made into 180 parts of solution.This solution is mixed with mixed powder, pinch through mixing, extrusion, make diameter and be 1.6 millimeters trilobal cross bar.At 120 ℃ down after dry 4 hours, 600 ℃ of roastings 4 hours make the carrier that contains zeolite with extrudate.
(2) take by weighing Xiao Suangu 0.16 gram, nickelous nitrate 3.63 grams are measured 10.8 milliliters of ammonium metatungstate solutions (with example 1), and 20.4 milliliters of magnesium nitrate solutions (with example 1) are made into 54 milliliters of co-impregnated solutions with water.Contained Zeolite support 4 hours with what this solution impregnation 69.4 gram steps (1) made, then 120 ℃ of dryings 4 hours, 500 ℃ of roastings 4 hours make catalyzer C provided by the invention
2Catalyzer C
2Middle nickel, cobalt, tungsten, magnesium oxide content and zeolite content are as shown in table 1.
Example 3
This example illustrates Preparation of catalysts provided by the invention.
(1) get 30 parts of REY zeolites (with example 1), 210 parts of pseudo-boehmites (with example 1), 9 parts of field mountain valley with clumps of trees and bamboo powder mix.Nitric acid and water that to measure 10 parts of concentration be 67 heavy % are made into 180 parts of solution.This solution under agitation is added in the mixed powder, and warp mixes and pinches, extrusion, and making diameter is 1.6 millimeters trilobal cross bars.At 120 ℃ down after dry 4 hours, 600 ℃ of roastings 4 hours make the carrier that contains zeolite with extrudate.
(2) take by weighing Xiao Suangu 0.16g, nickelous nitrate 1.8 gram is measured 54 milliliters of ammonium metatungstate solutions (with example 1), and 10.2 milliliters of magnesium nitrate solutions (with example 1) are made into 58.8 milliliters of co-impregnated solutions with water.The carrier that contains zeolite that makes with this solution impregnation 75.5 gram steps (1) 4 hours, then 120 ℃ of dryings 4 hours, 500 ℃ of roastings 4 hours make catalyzer C provided by the invention
3Catalyzer C
3Middle nickel, cobalt, tungsten, magnesium oxide content and zeolite content are as shown in table 1.
Example 4
This example illustrates Preparation of catalysts provided by the invention.
(1) take by weighing Xiao Suangu 0.24 gram, nickelous nitrate 5.46 grams are measured 16.2 milliliters of ammonium metatungstate solutions (with example 1), and 30.6 milliliters of magnesium nitrate solutions (with example 1) are made into 57.5 milliliters of co-impregnated solutions with water.Contain magnesium oxide gamma-alumina (content of magnesia 2 heavy %) 4 hours with this solution impregnation 96.6 grams, then 120 ℃ of dryings 4 hours, 500 ℃ of roastings 4 hours.
(2) get 30 parts of REY zeolites (with example 1), 70 parts of pseudo-boehmites (with example 1), 3 parts of blue or green powder in field mix.Nitric acid and water that to take by weighing 4 parts of citric acids and 3.2 parts of concentration be 67 heavy % are made into 60 parts of solution.This solution under agitation is added in the mixed powder, pinches through mixing, it is 1.6 millimeters trilobal cross bar that extrusion is made diameter.This extrudate is at 120 ℃ down after dry 4 hours, 600 ℃ of roastings 4 hours.
(3) product that step (1) and step (2) are obtained mixes by 1: 1 volume ratio, makes catalyzer C provided by the invention
4Catalyzer C
4Middle nickel, cobalt, tungsten, magnesium oxide content and zeolite content are as shown in table 1.
Example 5
This example illustrates Preparation of catalysts provided by the invention.
(1) prepares the carrier that contains zeolite by example 3 described methods.
(2) take by weighing Xiao Suangu 1.96 gram, measure 54 milliliters of ammonium metatungstate solutions (with example 1), 10.2 milliliters of magnesium nitrate solutions (with example 1) are made into 58.8 milliliters of co-impregnated solutions with water.The carrier that contains zeolite that makes with this solution impregnation 75.5 gram steps (1) 4 hours, then 120 ℃ of dryings 4 hours, 400 ℃ of roastings 4 hours make catalyzer C provided by the invention
5Catalyzer C
5Middle cobalt, tungsten, magnesium oxide content and zeolite content are as shown in table 1.
Example 6
This example illustrates Preparation of catalysts provided by the invention.
(1) prepares the carrier that contains zeolite by example 3 described methods.
(2) take by weighing nickelous nitrate 1.96 gram, measure 54 milliliters of ammonium metatungstate solutions (with example 1), 10.2 milliliters of magnesium nitrate solutions (with example 1) are made into 58.8 milliliters of co-impregnated solutions with water.The carrier that contains zeolite that makes with this solution impregnation 75.5 gram steps (1) 4 hours, then 120 ℃ of dryings 4 hours, 500 ℃ of roastings 4 hours make the catalyzer C that uses provided by the invention
6Catalyzer C
6Middle nickel, tungsten, magnesium oxide content and zeolite content are as shown in table 1.
Table 1
| Example number | 1 | DB1 | DB2 | 2 | 3 | 4 | 5 | 6 |
| The catalyzer numbering | C 1 | B 1 | B 2 | C 2 | C 3 | C 4 | C 5 | C 6 |
| Zeolite content, heavy % | 32.23 | - | 32.23 | 14.55 | 15.75 | 17.21 | 15.75 | 15.75 |
| Content of magnesia, heavy % | 3.28 | 3.28 | - | 3.07 | 1.53 | 2.78 | 1.53 | 1.53 |
| Tungsten oxide content, heavy % | 10.53 | 10.53 | 10.53 | 9.88 | 4.92 | 5.88 | 4.92 | 4.92 |
| Nickel oxide content, heavy % | 1.23 | 1.23 | 1.23 | 1.16 | 0.59 | 0.68 | - | 0.62 |
| Cobalt oxide content, heavy % | 0.06 | 0.06 | 0.06 | 0.05 | 0.03 | 0.04 | 0.62 | - |
| Nickel and tungsten atom ratio | 20.6 | 20.6 | 20.6 | 23.3 | 19.7 | 17.1 | - | - |
Example 7～14
Following example illustrates the catalytic performance of catalyzer provided by the invention.
In 50 milliliters of fixed-bed reactor, be respectively charged into particle diameter and be 0.25～0.44 millimeter catalyzer C
1～C
6Each 50 milliliters, under hydrogen dividing potential drop 1.6 MPas, 290 ℃ of temperature, hydrogen to oil volume ratio 300,2 hours-1 condition of liquid hourly space velocity, vulcanized 3 hours with the straight-run spirit that contains dithiocarbonic anhydride 2 heavy %, high-sulfur catalytically cracked gasoline shown in the switching table 2, under different reaction conditionss, this high-sulfur catalytically cracked gasoline is carried out hydro-upgrading, and reaction conditions and result list in table 3 and the table 4 respectively.
Wherein, the content of all kinds of hydrocarbon adopts gas chromatographic analysis in the product.Sulphur content * 100% in desulfurization degree=(in the raw material in sulphur content-product sulphur content)/raw material.Sulphur content adopts microcoulomb method (SH/T0253-9) to measure.Aromaticity content * 100% in aromatic hydrocarbons increment rate=(in the product in aromaticity content-raw material aromaticity content)/raw material.The RON of anti-knock index variation=product and MON sum 1/2nd with the RON of raw material and MON sum 1/2nd poor.RON and MON adopt high resolution gas chromatography to measure (referring to " petrochemical complex analytical procedure (RIPP test method) ", 243～246, Science Press, 1990).The bromine valency adopts coulometry to measure (referring to " petrochemical complex analytical procedure (RIPP test method) ", 172, Science Press, 1990).The weight of the weight/liquid starting material of liquid receipts=liquid product * 100%.
Comparative Examples 3～4 (DB3～DB4)
The catalytic performance of following Comparative Examples explanation reference catalyst.
Press the method for example 7, under identical condition identical stock oil is carried out hydro-upgrading, different just catalyst system therefors is respectively the reference catalyst B of Comparative Examples 1～2 preparation
1And B
2The results are shown in Table 3.
Table 2
| The stock oil title | The high-sulfur catalytically cracked gasoline |
| Density (20 ℃), g/ml | 0.729 |
| Sulphur content, ppm | 1470.0 |
| Nitrogen content, ppm | 16.5 |
| The bromine valency, gBr/100g | 54.1 |
| RON | 92.2 |
| MON | 80.1 |
| GC RON | 91.6 |
| GC MON | 79.3 |
| Boiling range, ℃ | |
| Initial boiling point | 39 |
| 10 body % | 56 |
| 50 body % | 91 |
| 90 body % | 156 |
| Do | 184 |
| Form body % | |
| Paraffinic hydrocarbons | 33.56 |
| Alkene | 25.98 |
| Naphthenic hydrocarbon | 8.09 |
| Aromatic hydrocarbons | 32.37 |
Table 3
| Example number | 7 | 8 | 9 | DB3 | DB4 |
| The catalyzer numbering | C 1 | C 1 | C 1 | B 1 | B 2 |
| Temperature of reaction, ℃ | 330 | 290 | 310 | 330 | 330 |
| The hydrogen dividing potential drop, MPa | 3.2 | 1.6 | 1.6 | 3.2 | 3.2 |
| Liquid hourly space velocity, hour -1 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 |
| Hydrogen to oil volume ratio | 150 | 150 | 150 | 150 | 150 |
| The bromine valency, gBr/100g | 12.1 | 20.1 | 13.8 | 2.1 | 15.7 |
| The aromatic hydrocarbons increment rate, % | 23.0 | 7.0 | 16.8 | 1.3 | 15.3 |
| Desulfurization degree, heavy % | 99.7 | 88.3 | 97.6 | 99.8 | 99.5 |
| Anti-knock index changes | -1.25 | -1.95 | -1.65 | -9.00 | -1.90 |
| Liquid is received, heavy % | 97.3 | 98.4 | 97.7 | 100.1 | 91.2 |
| Product is formed, body % | |||||
| Paraffinic hydrocarbons | 41.9 | 41.4 | 42.9 | 53.2 | 40.5 |
| Alkene | 7.0 | 13.1 | 8.0 | 1.7 | 9.2 |
| Naphthenic hydrocarbon | 11.3 | 10.9 | 11.3 | 12.3 | 13.0 |
| Aromatic hydrocarbons | 39.8 | 34.6 | 37.8 | 32.8 | 37.3 |
Table 4
| Example number | 10 | 11 | 12 | 13 | 14 |
| The catalyzer numbering | C 2 | C 3 | C 4 | C 5 | C 6 |
| Temperature of reaction, ℃ | 290 | 310 | 310 | 310 | 310 |
| The hydrogen dividing potential drop, MPa | 3.2 | 3.2 | 1.6 | 3.2 | 3.2 |
| Liquid hourly space velocity, hour -1 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 |
| Hydrogen to oil volume ratio | 150 | 450 | 150 | 450 | 450 |
| The bromine valency, gBr/100g | 11.0 | 12.6 | 8.9 | 13.6 | 12.8 |
| The aromatic hydrocarbons increment rate, % | 17.1 | 12.6 | 12.1 | 12.5 | 12.6 |
| Desulfurization degree, heavy % | 90.9 | 95.7 | 98.9 | 88.0 | 90.4 |
| Uprising index variation | -1.55 | -1.80 | -1.90 | -1.70 | -1.75 |
| Liquid is received, heavy % | 97.6 | 97.8 | 98.4 | 97.9 | 97.8 |
| Product is formed, body % | |||||
| Paraffinic hydrocarbons | 42.4 | 43.0 | 46.2 | 42.2 | 43.0 |
| Alkene | 6.5 | 7.2 | 5.0 | 8.0 | 7.3 |
| Naphthenic hydrocarbon | 13.2 | 13.4 | 12.6 | 13.4 | 13.3 |
| Aromatic hydrocarbons | 37.9 | 36.4 | 36.2 | 36.4 | 36.4 |
Claims (9)
1. a gasoline fraction hydrogenating and modifying catalyst that contains zeolite is characterized in that, this catalyzer contains one or more and the alumina host in molybdenum and/or tungsten, nickel and/or cobalt, auxiliary agent magnesium, macropore and the mesopore zeolite; In oxide compound and with the total catalyst weight is benchmark, the content of described molybdenum and/or tungsten is that the content of 3～20 heavy %, nickel and/or cobalt is that 0.3～2 heavy %, auxiliary agent Mg content are 1～7 heavy %, the content of described zeolite is 5～60 heavy %, and described auxiliary agent magnesium is present in the catalyzer with the form of oxide compound.
2. catalyzer according to claim 1 is characterized in that, this catalyzer contains one or more and the alumina host in tungsten, nickel and cobalt, auxiliary agent magnesium, macropore and the mesopore zeolite; In oxide compound and with the total catalyst weight is benchmark, and the content of tungsten is preferably 4～15 heavy %, and the content of nickel and cobalt is preferably 0.5～1.5 heavy %, wherein, the atomic ratio of nickel and cobalt is 5～80, and the content of magnesium is 1～5 heavy %, and the content of described zeolite is 10～35 heavy %.
3. catalyzer according to claim 2 is characterized in that, the atomic ratio of described nickel and cobalt is 10～30.
4. catalyzer according to claim 1 is characterized in that, described zeolite is one or more in faujusite, mordenite, ZSM-5 zeolite, Beta zeolite, the omega zeolite.
5. catalyzer according to claim 4 is characterized in that, described zeolite is one or more in y-type zeolite, ZSM-5 and the mordenite of Hydrogen or rare-earth type.
6. catalyzer according to claim 5 is characterized in that, described zeolite is the y-type zeolite of Hydrogen or rare-earth type.
7. catalyzer according to claim 6 is characterized in that, described zeolite is that lattice constant is the Hydrogen of 24.55～24.75 dusts or the y-type zeolite of rare-earth type.
8. catalyzer according to claim 1 is characterized in that, auxiliary agent magnesium, molybdenum and/or tungsten in the described catalyzer and nickel and/or cobalt load on the mixture that contains zeolite and aluminum oxide; Perhaps, auxiliary agent magnesium, molybdenum and/or tungsten in the described catalyzer and nickel and/or cobalt load on the aluminum oxide, and zeolite has an independent existence with the form of aluminum oxide and zeolite mixture.
9. catalyzer according to claim 1 is characterized in that, described gasoline fraction is catalytically cracked gasoline or coker gasoline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99122230A CN1094968C (en) | 1999-11-04 | 1999-11-04 | Gasoline fraction hydrogenating and modifying catalyst containing zeolite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99122230A CN1094968C (en) | 1999-11-04 | 1999-11-04 | Gasoline fraction hydrogenating and modifying catalyst containing zeolite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1295111A CN1295111A (en) | 2001-05-16 |
| CN1094968C true CN1094968C (en) | 2002-11-27 |
Family
ID=5282377
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99122230A Expired - Lifetime CN1094968C (en) | 1999-11-04 | 1999-11-04 | Gasoline fraction hydrogenating and modifying catalyst containing zeolite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1094968C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7557255B2 (en) | 2001-05-02 | 2009-07-07 | Bp Corporation North America Inc. | Method and an unleaded low emission gasoline for fueling an automotive engine with reduced emissions |
| CN101439293B (en) * | 2007-11-19 | 2011-03-16 | 中国石油天然气集团公司 | Selective hydrodesulfurization catalyst containing mesoporous molecular screen and preparation method thereof |
| CN102485332B (en) * | 2010-12-03 | 2013-10-16 | 中国石油天然气股份有限公司 | Distillate oil hydrogenation deacidification catalyst containing molecular sieve, its preparation and application |
| CN103184066B (en) * | 2011-12-28 | 2014-10-15 | 中国石油天然气股份有限公司 | Deacidification method for distillate oil |
| CN103285934A (en) * | 2012-03-01 | 2013-09-11 | 中国石油天然气股份有限公司 | Distillate oil hydrogenation deacidifcation catalyst carrier containing molecular sieve and preparation method of distillate oil hydrogenation deacidifcation catalyst carrier |
| CN110465325A (en) * | 2018-05-09 | 2019-11-19 | 中国石油化工股份有限公司 | Support type oxidation-desulfurizing catalyst molecular sieve and its preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5266188A (en) * | 1991-04-22 | 1993-11-30 | Amoco Corporation | Selective hydrotreating |
| CN1110304A (en) * | 1994-04-13 | 1995-10-18 | 中国石油化工总公司 | Heavy oil hydrotreatment catalyst |
| CN1184844A (en) * | 1996-12-10 | 1998-06-17 | 中国石油化工总公司 | Catalyst for hydrodesulfurization fraction oil |
| US5865988A (en) * | 1995-07-07 | 1999-02-02 | Mobil Oil Corporation | Hydrocarbon upgrading process |
-
1999
- 1999-11-04 CN CN99122230A patent/CN1094968C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5266188A (en) * | 1991-04-22 | 1993-11-30 | Amoco Corporation | Selective hydrotreating |
| CN1110304A (en) * | 1994-04-13 | 1995-10-18 | 中国石油化工总公司 | Heavy oil hydrotreatment catalyst |
| US5865988A (en) * | 1995-07-07 | 1999-02-02 | Mobil Oil Corporation | Hydrocarbon upgrading process |
| CN1184844A (en) * | 1996-12-10 | 1998-06-17 | 中国石油化工总公司 | Catalyst for hydrodesulfurization fraction oil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1295111A (en) | 2001-05-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1253993A (en) | Production method of low-sulfur gasoline | |
| WO2007135769A1 (en) | Process for producing hydrocarbon fraction | |
| CN1778873A (en) | Inferior diesel hydrogenation catalyst | |
| WO2019018224A1 (en) | Systems and methods for processing heavy oils by oil upgrading followed by refining | |
| CN1448481A (en) | Method for production of low sulfur and thiol content hydrocarbon | |
| JPH10505127A (en) | Gasoline reforming method | |
| CN1049679C (en) | Catalyst for hydrogenation conversion of diesel | |
| CN1094967C (en) | Gasoline fraction hydrogenating and modifying method | |
| CN1094968C (en) | Gasoline fraction hydrogenating and modifying catalyst containing zeolite | |
| CN1116387C (en) | Hydrocracking catalyst and hydrocracking method for hydrocarbon oils | |
| JP4590407B2 (en) | Production of low sulfur naphtha products by improved olefin isomerization | |
| CN1903993A (en) | Hydrogenation cracking method to produce more raw material for making ethylene | |
| CN1283761C (en) | Hydrogenation modification process for low grade gasoline | |
| CN1204231C (en) | Desulfurization process of gasoline | |
| CN1173010C (en) | Method and catalyst for selective hydrogenation refining of cracked gasoline | |
| CN1896190A (en) | Hydrogenation modified catalyst of Fischer-Tropsch synthetic oil and its production | |
| CN1255513C (en) | Isomerization catalyst and preparation thereof | |
| CN1218021C (en) | Gasoline hydrogenation catalyst, its prep. and application in lowering olefin by desulfurization | |
| JP2003520889A5 (en) | ||
| CN1524930A (en) | Light hydrocarbon non-hydrogenation modified catalyst, preparing process and application thereof | |
| CN1552819A (en) | Light hydrocarbon hydrogenation method | |
| CN101407731B (en) | Hydrotreating process for producing low-sulfur oil | |
| CN1246519A (en) | Method for producing high cetane value and low sulfur content diesel oil | |
| CN1055951C (en) | Method of hydrogenation conversion for masrolar D | |
| CN1231560C (en) | Naphtha selective hydrogenation desulfurization process and catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C53 | Correction of patent for invention or patent application | ||
| CB02 | Change of applicant information |
Applicant after: China Petrochemical Group Corp. Applicant after: Sinopec Research Institute of Petroleum Processing Applicant before: China Petrochemical Group Corp. Applicant before: Chinese petrochemical industry Research Institute of Petro-Chemical Engineering of group company |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: CHINA PETROCHEMICAL CORPORATION; CHINA PETROLEUM + CHEMICAL CORPORATION, PETROLEUM CHEMICAL ENGINEERING INSTITUTE TO: CHINA PETROCHEMICAL CORPORATION; CHINA PETROCHEMICAL GROUP PETROCHEMICAL SINCE INSTITUTE |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20021127 |
|
| CX01 | Expiry of patent term |