CN101177619A - Method for producing diesel oil and chemical materials by f-t synthetic wax - Google Patents
Method for producing diesel oil and chemical materials by f-t synthetic wax Download PDFInfo
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- CN101177619A CN101177619A CNA2007100901243A CN200710090124A CN101177619A CN 101177619 A CN101177619 A CN 101177619A CN A2007100901243 A CNA2007100901243 A CN A2007100901243A CN 200710090124 A CN200710090124 A CN 200710090124A CN 101177619 A CN101177619 A CN 101177619A
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Abstract
The invention discloses a method for producing chemical raw material and diesel oil by Fischer-Tropsch synthetic wax and the method is that the Fischer-Tropsch synthetic wax and hydrogen gas contact with hydrogen cracking catalyst under hydrogen cracking condition and then the reaction products are treated by fractionation; diesel distillate obtained is the clean diesel with a low freezing point, while the naphtha cut obtained is high-quality raw material used for cracking of steam to ethane, and distillation range is higher than the hydrogen cracking of tail oil circulation of the diesel oil, wherein, the hydrogen cracking catalyst is the hydrogen cracking catalyst containing Beta zeolite and the weight content of the Beta zeolite in the catalyst is 0.5 percent to 60 percent; the Beta zeolite has properties that SiO2/Al2O3 molar ratio is 20 to 150 and Na2O less than or equal to 0.2w percent. The method of the invention can prepare the Fischer-Tropsch synthetic wax into the clean diesel oil with a low freezing point and high-quality raw material used for producing ethylene by steam cracking.
Description
Technical field
The present invention relates to a kind of method of producing diesel oil and industrial chemicals, particularly adopt new catalyst to make, f-t synthetic wax is processed as the method for clean diesel and industrial chemicals hydrocracking by f-t synthetic wax.
Background technology
Fossil oil mainly comprises coal and oil, and from world wide, the reserves of coal far surpass reserves.Therefore, how substituting oil with coal is the important topic of energy field.The important course of processing that coal substitutes oil is the liquidation of coal process, and the further processing treatment process of gelatin liquefaction product.
According to the different routes of chiral process, coal liquefaction can be divided into direct liquefaction and indirect liquefaction two big classes.DCL/Direct coal liquefaction is that coal is directly changed into liquid product.Its technology mainly contains Exxon (Exxon) Exxon donor solvent process (being called for short the EDS method), H-coal process etc.The EDS method is the effect by hydrogen supply dissolvent, under certain temperature and pressure coal hydrogenation is liquefied as liquid fuel; H-coal process is to adopt the pressurized catalysis fluidized-bed reactor, by the effect of high temperature and catalyzer, makes coal be cracked into micromolecular liquid hydrocarbon fuel under hydrogen pressure.The diesel yield of Hydrogenation liquefaction process is about 70%, LPG and gasoline account for 20%, and all the other also contain heteroatomss such as a considerable amount of oxygen, nitrogen, sulphur for the intermediates based on polycyclic aromatic hydrocarbons, aromaticity content is also higher, further is processed as products such as high-quality gasoline, diesel oil than difficulty.
CN1382772A has introduced a kind of method from coal direct liquefaction oil greatly preparing hihg-quality diesel oil or rocket engine fuel, liquefied coal coil stable hydrogenation after the filtration, then diesel oil distillate, the tail oil cut that obtains carried out the deep hydrogenation upgrading, separate the hydro-upgrading reactor effluent and obtain gas, naphtha fraction, diesel oil distillate and tail oil cut or gas, naphtha fraction, rocket engine fuel, diesel oil distillate and tail oil cut, hydrogen rich stream recycles, and part tail oil cut loops back coal liquefaction system as hydrogen supply agent.
CN1493663A has introduced a kind of combined technical method of being produced fine-quality diesel oil by coal direct liquefaction oil, liquefied coal coil stable hydrogenation after the filtration, to obtain diesel oil distillate then and carry out hydro-upgrading, and separate the hydro-upgrading reactor effluent and obtain naphtha fraction, diesel oil distillate.Because the coal direct liquefaction oil aromaticity content is higher, the cetane value of the diesel oil distillate that above-mentioned two kinds of methods obtain only can reach about 45, can not satisfy Europe II diesel oil standard.
ICL for Indirect Coal Liquefaction be coal at high temperature with oxygen and water vapour reaction decomposes, make coal all be gasificated into unstripped gas (CO+H
2Mixture), under the effect of catalyzer, further synthesize liquid oil or petroleum chemicals again.At present, indirect liquefaction has been realized industrial production in many countries, mainly divides two kinds of production technique, the one, and fischer-tropsch (Fischer-Tropsch) synthesis technique is with the direct synthetic oil of unstripped gas; The 2nd, the Bill that rubs (Mobil) technology by the unstripped gas synthesizing methanol, becomes gasoline by methanol conversion again.Wherein fischer-tropsch is synthetic is the processing method with better prospect.In the last running of Fisher-Tropsch synthesis fuels, mainly be made up of straight-chain paraffin, condensation point is very high, claims f-t synthetic wax usually, generally is difficult to direct utilization, need further be processed as various products.
CN1594509A etc. adopt the catalyst based hydrocracking that carries out of Fe with the heavy hydrocarbon and/or the kettle bottom wax of Fisher-Tropsch synthesis fuels in suspension bed, produce petroleum naphtha and diesel product.Concrete grammar is that catalyst based and Fischer-Tropsch synthesis of heavy hydrocarbon of Fe and/or kettle bottom wax raw material are mixed at storage tank, is mixed and heated to 300～400 ℃ with hydrogen then and enters suspended-bed reactor, carries out hydrocracking; The reaction conditions of hydrocracking is 3.0～20.0MPa, and temperature of reaction is 350～500 ℃, and hydrogen to oil volume ratio is 300～1800, and the liquid air speed is 0.1～3.0h
-1The hydrogenation performance of suspension bed technology a little less than, severe reaction conditions, product property needs further to improve.
USP6,475,375, USP6,656,343 grades have been introduced and a kind of Fisher-Tropsch synthesis fuels have been converted into the method for compression ignition type (CI) engine with naphtha fuel or its blending component.Concrete grammar is, the naphtha fraction of Fisher-Tropsch synthesis fuels is carried out hydrotreatment, hydrocracking is carried out in the last running of Fisher-Tropsch synthesis fuels, the petroleum naphtha that petroleum naphtha after the hydrotreatment and hydrocracking obtain is as fuel or its blending component of compression ignition engine, the controlling index of these petroleum naphthas is: final boiling point is lower than 160 ℃, cloud point is below-30 ℃, and cetane value is more than 30.But naphtha fraction is not the ideal fuels of compression ignition engine, and with its concocted diesel oil, though can reduce its condensation point, other index such as flash-point etc. will be affected.
USP5,689,031 introductions are the method for diesel oil with Fisher-Tropsch synthesis fuels production.Propose to keep a small amount of oxygenatedchemicals (thinking the alcohols that C12 is above) in the Fisher-Tropsch synthesis fuels, can improve the lubricity of combined diesel oil, needn't add expensive additive during use, simultaneously in order to reduce condensation point, all components need be carried out hydroisomerization.Concrete grammar is, Fisher-Tropsch synthesis fuels is separated into heavier cut and lighter cut, further this lighter cut is separated, and heavier cut and be lower than about 500 lighter cut and carry out hydroisomerization is the product of this isomery and the not part of hydrotreatment (being generally 500～700 cuts) blending.This patent provides a kind of method of improving the combined diesel oil lubricity, but operation is comparatively complicated.
USP5,378,348 propose a kind of Fisher-Tropsch synthesis fuels mainly to be produced method into rocket engine fuel.At first be light naphtha fraction, kerosene(oil)fraction (320～500) and 500 with the Fisher-Tropsch synthesis fuels fractionation
+With kerosene(oil)fraction hydrotreatment hydroisomerizing then, produce and be the high quality synjet.With 500 °F
+Cut fraction hydrogenation isomery (having the cracking function), kerosene(oil)fraction that obtains and virgin kerosene cut carry out hydrotreatment and hydroisomerizing jointly, and the diesel oil distillate that obtains is as product, 700 °F
+The cut circulation.Lock out operation in this flow process is more, and long flow path, energy consumption are big.In addition, though the kerosene(oil)fraction foreign matter content that Fisher-Tropsch synthesis fuels obtains is lower, its smoke point is difficult to be improved, and the cost that is processed as the high quality rocket engine fuel is higher.
USP6,589,415 and USP6,583,186 have introduced the method for Fisher-Tropsch synthesis fuels being carried out hydrocracking, and its principal feature is that hydrocracking is carried out in the last running of synthetic oil, with the lighting end of the synthetic oil cooling logistics as the hydrocracking reaction bed.Its main deficiency is as can be seen, and the synthetic oil raw material that enters hydrocracking does not pass through hydrotreatment, wherein contains a certain amount of impurity (as oxygen), and these impurity generally are the objectionable impuritiess of hydrocracking catalyst, can cause the permanent deactivation of catalyzer.In addition, the lighting end of synthetic oil also enters hydrocracking reactor, and consequently liquid product yield can reduce.
USP4,080,397 and USP4,059,648 introduction such as grade is the method for stop bracket gasoline with Fisher-Tropsch synthesis fuels production.Detailed process is for to carry out hydrotreatment with Fisher-Tropsch synthesis fuels, and the last running after the hydrotreatment adopts the selective splitting catalyzer that contains ZSM system molecular sieve to handle, and the gasoline fraction that obtains has higher octane value.But with the Fisher-Tropsch synthesis fuels is that the raw material production stop bracket gasoline does not have reasonableness economically, show that mainly liquid product yield is low, gasoline octane rating improves limited (generally only being about 85), and the diesel oil distillate that this process obtains is second-rate, should not directly use.
USP4,684,756 have introduced a kind of method of producing premium-type gasoline with f-t synthetic wax.Principal feature is to adopt the fluidized-bed process process, adopts the hydrocracking catalyst or the catalyst for hydrogenation de-waxing of catalytic cracking catalyst or low hydrogenation performance, f-t synthetic wax is cracked into the split product that is rich in alkene.The split product that will be rich in alkene then carries out oligomerisation reaction, obtains high quality (high-octane rating) gasoline.This method is a purpose to produce gasoline, and reaction process is comparatively complicated.
CN1125960A etc. adopt extraordinary amorphous aluminum silicide carried noble metal, are lubricant base with Fisher-Tropsch synthesis fuels production.Wherein catalyzer is by precious metal and the specific surface 100～500m of 0.05～10wt%
2The silica/alumina carrier of/g constitutes.USP4,500,417 handle f-t synthetic wax under certain condition with the catalyzer that contains the β zeolite, to produce distillate and lubricant base.USP5,362,378 adopt the low acidic beta zeolite catalyzer of boron modification of load platinum to carry out hydroisomerizing, and the distillate that obtains is as diesel oil distillate, and lubricant base is produced in further isomerization dewaxing of last running or solvent dewaxing.USP5,882,505 and CN96121776.6 etc. also be to be raw material with the Fisher-Tropsch synthesis fuels, produce lubricant base.As mentioned above, be that the pertinent literature of raw material production lubricant base is more with the Fischer-Tropsch synthesis oil, but straight chain hydrocarbon content is more in the f-t synthetic wax, not the desirable feedstock source of lubricant base.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of method for hydrogen cracking of f-t synthetic wax is provided, using this method can will mainly be made up of straight chain hydrocarbon, the f-t synthetic wax that is difficult to directly to utilize is processed as low product and the high-quality industrial chemicals of coagulating of fine diesel oil, thereby opened up the approach of a fischer-tropsch synthesis product comprehensive utilization, improved the total output of coal chemical industry greatly.
The purpose of this invention is to provide a kind of method of producing diesel oil and industrial chemicals by f-t synthetic wax, this method comprises the steps: under hydrocracking condition, the f-t synthetic wax raw material is contacted with hydrocracking catalyst with hydrogen, the hydrocracking reaction product is carried out fractionation, the petroleum naphtha that obtains, diesel oil and tail oil cut, wherein said naphtha fraction is the raw material of high quality steam cracking ethylene preparation, diesel oil distillate is low condensation point clean diesel, and boiling range is higher than capable of circulation time hydrocracking process of tail oil of diesel oil.
In the method for the invention, described f-t synthetic wax is the heavier cut in the liquid product that obtains in the fischer-tropsch building-up process, and its initial boiling point is generally 300～400 ℃, contains C usually
19 +Hydrocarbon molecules.
In the method for the invention, described fractionation operation can be carried out product separation as required, generally can be separated into petroleum naphtha, diesel oil and tail oil, the cut point of petroleum naphtha and diesel oil can be 120～260 ℃, and the cut point of diesel oil and tail oil can be 330～385 ℃.Described naphtha fraction is as the raw material of preparing ethylene by steam cracking, and the diesel oil distillate cetane value is greater than 60, and condensation point is lower than-50 ℃, can be used as high-grade low-freezing diesel oil.
In the method for the invention, the operational condition of described hydrocracking is 3～20MPa for the hydrogen dividing potential drop, and temperature is 300～450 ℃, and volume space velocity is 0.1～20h-1 during liquid, and hydrogen to oil volume ratio is 200～3000; Preferably, the operational condition of described hydrocracking is: the hydrogen dividing potential drop is 5～15MPa, and temperature is 320～430 ℃, and volume space velocity is 0.2～10h-1 during liquid, and hydrogen to oil volume ratio is 400～2000.
Temperature of reaction described in the inventive method is meant average reaction temperature.
Another object of the present invention has provided a kind of new hydrocracking catalyst.Up to the present, existing hydrocracking catalyst all is the type that is applicable to the natural oil complete processing basically, various problems can occur when using it for the hydrocracking of Fisher-Tropsch synthesis fuels, wax etc. of various cuts, resulting product and production efficiency all can not satisfy the production needs.Hydrocracking catalyst of the present invention is highly suitable for the hydrocracking of Fisher-Tropsch synthesis fuels, wax of various cuts etc., particularly can obtain fine-quality diesel oil and other industrial chemicals by the f-t synthetic wax that prior art is difficult to utilize, thereby overcome a great problem of prior art.
Hydrocracking catalyst of the present invention is a kind of dual-function catalyst, and this catalyzer is made up of metal hydrogenation component, acid cracking component and carrier.Gross weight in catalyzer, described metal hydrogenation component is in oxide form, its weight content in catalyzer is 0.1%～40%, and the weight content of acid cracking component in catalyzer is 0.5%～60%, and the weight content of carrier in catalyzer is 10%～80%.
In hydrocracking catalyst of the present invention, the weight content of wherein said acid cracking component in catalyzer is preferably 2%～30%, described acid cracking component can be an acid cracking component commonly used in this type of catalyzer, be preferably the β zeolite, more preferably have the β zeolite of following character: Si
O2/Al
2O
3Mol ratio is 20～150, and mean particle size is 0.1-0.5 μ m, specific surface 500-750m
2/ g, infrared acidity is 0.1～0.5mmol/g, Na
2O≤0.2w%, pore volume are 0.35-0.50ml/g; Wherein the aperture is that the hole of 0.1～1.7nm accounts for 20%～50% of total pore volume, and the aperture accounts for 5%～20% of total pore volume for the hole of＞1.7～6.0nm, the aperture be the hole of 10.0～90.0nm account for total pore volume 30%～60%.Particularly preferred β zeolite should have following character: SiO
2/ Al
2O
3Mol ratio is at 80-120, Na
2O≤0.15w%.
Metal hydrogenation component described in the hydrocracking catalyst of the present invention is preferably selected from one or more in group vib or the VIII family base metal, also can be in the VIII family precious metal one or more, described precious metal and base metal can use respectively or use simultaneously.Wherein said group vib base metal is selected W and/or Mo usually; VIII family base metal is selected Co and/or Ni usually; VIII family precious metal is selected Pt and/or Pd usually.Wherein in the gross weight of catalyzer, base metal is preferably 10%～30% in the weight content of oxide compound in catalyzer; Precious metal is preferably 0.2%～2% in the weight content of element in catalyzer.
Carrier described in the hydrocracking catalyst of the present invention can be a carrier commonly used in this type of catalyzer, and porous refractory oxide preferably is as in amorphous aluminum silicide, aluminum oxide, silicon oxide, clay and the Y zeolite etc. one or more.In the gross weight of catalyzer, the weight content of carrier in catalyzer is preferably 15%～60%.
The β zeolite with multi-stage artery structure that hydrocracking catalyst of the present invention is related can prepare according to following method: silicon source and aluminium source are in the presence of the tetraethyl ammonium hydroxide template, with two sections crystallization of hydrothermal method, elder generation's low temperature nucleation, back high temperature crystallization, or adopt a step crystallization; Add ammonium salt and handle, filter then, drying, roasting removes organic ammonium, and through peracid treatment and High Temperature High Pressure hydrothermal treatment consists, makes the β zeolite product of multistage pore canal.
Concrete, the β zeolite with multi-stage artery structure that hydrocracking catalyst of the present invention is related can prepare according to following method: silicon source and aluminium source are in the presence of the tetraethyl ammonium hydroxide template, with two sections crystallization of hydrothermal method, first low temperature nucleation, back high temperature crystallization, or adopt the single stage method crystallization; Add ammonium salt and handle certain hour, above-mentioned crystallization and ammonium salt are handled and are carried out under continuously stirring; Filter then, wash and dry, divide three sections temperature control roastings to remove organic ammonium, and acid treatment under the mitigation condition and High Temperature High Pressure hydrothermal treatment consists, make the β zeolite product of multistage pore canal.
More specifically, the β prepare zeolite process that relates to of catalyzer of the present invention is as follows:
(1) crystallization in silicon source and aluminium source: the porosu solid silica gel particle is adopted in the silicon source, sodium aluminate is adopted in the aluminium source, template adopts tetraethyl ammonium hydroxide and sodium hydroxide and water to mix, adopt two sections crystallization methods, elder generation's low temperature nucleation, back high temperature crystallization, in crystallizing kettle in 90～130 ℃ of following crystallization 10～40 hours, at 110-170 ℃ of following crystallization 20-50 hour, or 100 ℃-170 ℃ crystallization 10-60 hour.
(2) ammonium salt is handled: directly add ammonium salt therein and handled 0.2～3.0 hour down in 80～120 ℃, ammonium salt is handled and can be carried out 1～3 time, and the concentration of ammonium salt in mixture is 0.5～3mol/L.
(3) aftertreatment: filter after ammonium salt is handled, wash, drying, remove organic ammonium by three sections temperature control roastings, low temperature (150-250 ℃) dehydration 1.0～6.0 hours, middle temperature (250-450 ℃) organic ammonium decomposed 1.0～4.0 hours, and high temperature (450-650 ℃) was removed uncombined carbon 6.0～20.0 hours.
(4) acid treatment and High Temperature High Pressure hydrothermal treatment consists: acid treatment be 0.1-5.0mol/L (carry out in preferred 0.5～1.5mol/L) the mineral acid, temperature 20-100 ℃, treatment time 1.0-3.0 hour; The High Temperature High Pressure hydrothermal treatment consists is at temperature 500-700 ℃, carries out under the pressure 0.05-0.5Mpa, handles 0.5-5.0 hour, obtains the beta zeolite with multilevel pore canals particulate product.
Wherein the feed ratio of each raw material (mole) is: Na
2O/Al
2O
3Be 0.5-5.0, be preferably 1.0-2.0; (TEA)
2O/Al
2O
3Be 0.5-5.0, be preferably 1.0-3.0; SiO
2/ Al
2O
3Be 10-100, be preferably 10-50; H
2O/Al
2O
3Be 100-500; Be preferably 100-300.Above-mentioned Na
2O obtains Al by sodium hydroxide in the raw material and sodium aluminate conversion
2O
3Be to obtain SiO by sodium aluminate conversion in the raw material
2Obtain by solid silicone conversion in the raw material.
Said porosu solid silica gel in the β prepare zeolite process that catalyzer of the present invention relates to, can be gross porosity, mesopore, the silica gel of pore, said aluminium source can be solid sodium aluminate and liquid sodium aluminate, and the sodium source can be the mixture of sodium aluminate or sodium aluminate and sodium hydroxide.Said template tetraethyl ammonium hydroxide is from etamon chloride or tetraethyl-amine bromide.Ammonium salt can be ammonium chloride, ammonium nitrate or ammonium sulfate, also can be mixed-ammonium salt.The mineral acid that acid treatment is used is generally hydrochloric acid, nitric acid or sulfuric acid etc.
Hydrocracking catalyst of the present invention can be according to the routine techniques preparation of catalyst field, as adopting method preparations such as pickling process, coprecipitation method; Also can adopt disclosed patented method preparation in this area, as adopting disclosed method preparation in CN1054153C, CN1108356C, CN1107710C, CN1151238C, the patent documentations such as CN1147574C, CN1219031C.
Before use, must vulcanize or reduce processing, make that metal component changes sulfide or simple substance form in the catalyzer, to improve the hydrogenation activity of catalyzer hydrocracking catalyst of the present invention.Sulfuration or method of reducing are method well known to those skilled in the art.
In addition, employed hydrocracking catalyst also can adopt the known commercial catalyst of prior art to realize in the method for hydrogen cracking of f-t synthetic wax of the present invention, and just result of use is not as good as catalyzer of the present invention.
Because the sulphur nitrogen impurity is extremely low in the f-t synthetic wax, the present invention selects a kind of hydrocracking catalyst that contains the beta-molecular sieve of suitable character for use, isocrackate fractionation gained naphtha fraction is a high quality steam cracking ethylene preparation raw material, the diesel oil distillate cetane value is not less than 60, condensation point is lower than-50 ℃, the sulphur nitrogen content is extremely low, is high-quality low freezing point fuel, the cracking that can circulate of unconverted tail oil part.It is low that the present invention takes into full account f-t synthetic wax sulphur nitrogen impurity, the main characteristics of forming by straight-chain paraffin, used beta-molecular sieve has cracking and isomerization is difunctional, at cracked simultaneously, can promote the C-C chain transfer of carbonyl positive ion and produce more side chain, hydrocracking gained condensation point of diesel oil is very low, can satisfy the demand of oil product market to low-coagulation diesel oil.Selection has the β zeolite that enriches secondary pore, can improve the rapid diffusion of resultant of reaction, reduces secondary reaction, improves the yield of diesel oil distillate.Particularly adopt to have the less β zeolite of crystal grain, when further improving activity of such catalysts, can further reduce second pyrolysis, reduce gas yield, improve diesel yield with multiple pore distribution.
The gained diesel cetane-number of the inventive method gained is not less than 60, and condensation point is lower than-50 ℃, and the sulphur nitrogen content is extremely low, is high-quality low freezing point fuel.The inventive method gained naphtha fraction is a high quality steam cracking ethylene preparation raw material, and yield of ethene can reach 37%～39%, and the yield of ethene of common petroleum naphtha only is about 27%～28%.
Embodiment
Below in conjunction with embodiment the present invention is further detailed, but the protection domain that does not limit the present invention in any way.The infrared acidity that wherein relates to zeolite is the total acid content of 160 ℃ of pyridine IR-TPD, and specific surface area and pore volume adopt low-temperature nitrogen adsorption method to measure.The per-cent that relates to is weight percentage.
Embodiment 1～4The catalytic hydrocracking of f-t synthetic wax
Raw materials used character sees Table 1.Used hydrocracking catalyst character sees Table 2.Hydrocracking operational condition and product distribute and character sees Table 3.Tail oil loops back hydrocracking and refers to all or part of circulation, adopts whole round-robin operating method among the embodiment.Before carrying out hydrocracking reaction, hydrocracking catalyst is carried out prevulcanized, wherein reactive metal becomes sulphided state from oxidation state.Concrete operations are in reactor, with the hydrogen of sulfide hydrogen 0.8% (V) 200 ℃ of following constant temperature 5 hours, 320 ℃ of following constant temperature 10 hours.The hydrogen volume air speed is 1000h
-1, pressure is 5MPa.
Table 1 stock oil character
| Stock oil | Synthetic wax 1 | Synthetic wax 2 |
| Density/gm -3 | 0.8603 | 0.8625 |
| Boiling range/℃ | 321～550 | 381～650 |
| Acidity/mgKOH (100mL) -1 | 0.78 | 0.65 |
| Oxygen level, % | 0.2 | 0.1 |
The composition of table 2 hydrocracking catalyst
| Catalyzer | HC-CAT1 | HC-CAT2 | HC-CAT3 | HC-CAT4 |
| The Preparation of Catalyst source | CN1107710C embodiment 3 | CN1107710C embodiment 5 | CN1147574C embodiment 7 | CN1147574C embodiment 8 |
| Chemical constitution/wt% | ||||
| WO 3 | 20 | 22 | 22.5 | 22.5 |
| NiO | 5.5 | 7 | 7.5 | 7.5 |
| The β zeolite | 10 | 40 | 3 | 10 |
| Other carrier | Surplus | Surplus | Surplus | Surplus |
The character of table 3 embodiment 1～4 operational condition and products obtained therefrom
Embodiment 5～8The preparation of hydrocracking catalyst and the catalytic hydrocracking of f-t synthetic wax
Prepare the β zeolite according to following method, and prepare the hydrocracking catalyst of the inventive method, carry out the catalytic hydrocracking reaction of f-t synthetic wax then with prepared catalyzer with this β zeolite.
1, preparation modified beta zeolite
(1) modified beta zeolite B-1 preparation
(the laboratory preparation contains Al with the 78g sodium aluminate
2O
319.9m% contains Na
2O 21.44m%), (Haiyang Chemical Plant, Qingdao produces, and contains SiO for the 435g tetraethyl ammonium hydroxide aqueous solution (industrial product, concentration 1.4N), silochrom particle 288g
295%) and after water purification 120g mixes, fully 100 ℃ of reactions 20 hours in 2 liter stainless steel cauldrons under the continuous stirring condition, rise to 150 ℃ of crystallization 40 hours again, crystallization finishes release, cooling, add ammonium nitrate solution, by ammonium nitrate concn in the system is 2mol/L, stirs at 95 ℃ of constant temperature and filters then in 1 hour, carries out an ammonium salt again by above-mentioned condition and handles.Filter washing, drying then, remove organic ammonium by three sections temperature control roastings, the dehydration in 2 hours of 200 ℃ of constant temperature, 400 ℃ were decomposed organic ammonium 3 hours, 550 ℃ were decomposed free charcoal 12 hours, acid-treated concentration of hydrochloric acid 0.5mol/L, and fully agitation condition was handled 1 hour for following 80 ℃, filter washing, drying then, 650 ℃ of high-temperature high pressure water thermal treatment temps, pressure 0.1MPa handled 2 hours, promptly obtained β zeolite B-1 of the present invention.
The physico-chemical property of this β zeolite is: SiO
2/ Al
2O
3Be 102 (mol ratios), mean particle size is 0.25 μ m, and pore volume is 0.407ml/g, the aperture be the hole of 0.1～1.7nm account for total pore volume 32.2%, the aperture accounts for 8.2% of total pore volume for the hole of＞1.7～6.0nm, the aperture be the hole of 10.0～90.0nm account for total pore volume 54.5%.
(2) modified beta zeolite B-2 preparation
(the laboratory preparation contains Al with the 80g sodium aluminate
2O
318.90m% contains Na
2O 24.11m%), (Haiyang Chemical Plant, Qingdao produces and contains SiO for the 382g tetraethyl ammonium hydroxide aqueous solution (Industrial products, concentration 1.55N), silochrom particle 280g
295.2m%) mix with water purification 158g.Other conditions promptly obtain β zeolite B-2 with the B-1 preparation process.
The physico-chemical property of this β zeolite is: SiO
2/ Al
2O
3Be 98 (mol ratios), mean particle size is 0.20 μ m, and pore volume is 0.412ml/g, the aperture be the hole of 0.1～1.7nm account for total pore volume 28.9%, the aperture accounts for 12.3% of total pore volume for the hole of＞1.7～6.0nm, the aperture be the hole of 10.0～90.0nm account for total pore volume 54.4%.
(3) modified beta zeolite B-3 preparation
Ammonium salt is handled and used ammonium chloride, the concentration in system is 0.8mol/L, and temperature is 105 ℃, and the time is 2 hours, and number of times is 3 times.Nitric acid is used in acid treatment, and concentration is at 1.2mol/L, 50 ℃ of treatment temps, and in 1.5 hours treatment times, the High Temperature High Pressure hydrothermal treatment consists is 550 ℃ of temperature, and pressure 0.2MPa handled 3.0 hours, and other is with the B-1 preparation process, and getting product is B-3.
The physico-chemical property of this β zeolite is: SiO
2/ Al
2O
3Be 104 (mol ratios), mean particle size is 0.35 μ m, and pore volume is 0.409ml/g, the aperture be the hole of 0.1～1.7nm account for total pore volume 28.4%, the aperture accounts for 14.3% of total pore volume for the hole of＞1.7～6.0nm, the aperture be the hole of 10.0～90.0nm account for total pore volume 43.4%.
2, the preparation of hydrocracking catalyst
Use the modified beta zeolite with multi-stage artery structure of method for preparing to prepare following hydrocracking catalyst.
(1) preparation of hydrocracking catalyst HC-CAT5
Get modified beta zeolite B-1 8g (butt), amorphous aluminum silicide (SiO
2Content be 45w%, pore volume is 0.75ml/g, specific surface area is 390m
2/ g) 20g (butt) and aluminum oxide (specific surface area 240m
2/ g, pore volume 1.1mL/g) 12g (butt) mixes, and adds concentration by 80ml and be 3% little porous aluminum oxide (the specific surface area 240m of dilute nitric acid solution peptization 30g (butt)
2/ g, pore volume 0.5mL/g) tackiness agent that obtains continues to mix and pinches up to becoming paste, and extruded moulding, institute's moulding bar that obtains be 110 ℃ of dryings 8 hours down, 500 ℃ activate 4 hours and make activated carrier after.Again with the dissolving of the phosphoric acid of 24g molybdenum oxide, 6.8g basic nickel carbonate, 3.57g 85% and demarcate to 55mL, obtain the Mo-Co-P co-impregnated solution, flood the carrier of above-mentioned preparation, again 110 ℃ of dryings 8 hours with this steeping fluid, and 500 ℃ of activation obtained catalyzer HC-CAT5 after 4 o'clock.Catalyzer finally consists of: β zeolite 8wt%, amorphous aluminum silicide 20wt%, aluminum oxide 42wt%, cobalt oxide 3.8wt%, molybdenum oxide 24wt%, Vanadium Pentoxide in FLAKES 2.2wt%.
(2) preparation of hydrocracking catalyst HC-CAT6
Get modified beta zeolite B-2 12g (butt), aluminum oxide (specific surface area 400m
2/ g, pore volume 1.1mL/g) 18g (butt) and amorphous aluminum silicide (SiO
2Content be 65w%, pore volume is 0.58ml/g, specific surface area is 340m
2/ g) 40g (butt) mixes, and adds concentration by 80ml and be rare nitric acid of 3%, continues to mix and pinches up to becoming paste, extruded moulding, institute's moulding bar that obtains be 110 ℃ of dryings 8 hours down, 500 ℃ activate 4 hours and make activated carrier after.With the steeping fluid room temperature of tungstenic, nickel dipping 4 hours, 130 ℃ of dryings 3 hours were warmed up to 460 ℃ of roastings 5 hours, obtain catalyzer HC-CAT6.Catalyzer finally consists of: β zeolite 12wt%, aluminum oxide 20wt%, amorphous aluminum silicide 42wt%, nickel oxide 4wt%, Tungsten oxide 99.999 22wt%.
(3) preparation of hydrocracking catalyst HC-CAT7
Get modified beta zeolite B-3 34g (butt), (lattice constant is 2.443nm to Y zeolite, and silica alumina ratio is 8.43, and the sodium weight content is 0.12%, and 160 ℃ of total acid contents of pyridine IR-TPD are 1.170mmol/g, and specific surface area is 828m
2/ g, degree of crystallinity 96%, the hole of＞1.7 * 10-9m account for total hole 46%) 23g and aluminum oxide (specific surface area 240m
2/ g, pore volume 1.1mL/g) 15g adds concentration by 80ml and is 3% dilute nitric acid solution, and continue to mix and pinches up to becoming paste, extruded moulding, institute's moulding bar that obtains is 110 ℃ of dryings 8 hours down, and 500 ℃ of roastings got carrier in 4 hours.Vehicle group becomes: β zeolite 50wt%, Y zeolite 31wt%, aluminum oxide 19wt%.Carrier floods with nickel nitrate solution, and then 110 ℃ of dryings 3 hours, 550 ℃ of roastings are after 2 hours, with Pd (NH
4) NO
3Solution impregnation, again 110 ℃ of dryings 3 hours, 550 ℃ of roastings are after 4 hours, obtain the Pd weight content and be 0.8%, the Ni weight content is 3.5% catalyzer HC-CAT7.
3, the catalytic hydrocracking of f-t synthetic wax
Raw materials used character sees Table 1.Hydrocracking operational condition and product distribute and character sees Table 4.Use the described raw material of table 1, carry out hydrocracking reaction according to the described method of table 4, and reaction result is compared.
Before carrying out hydrocracking reaction, hydrocracking catalyst HC-CAT5, HC-CAT6 are carried out prevulcanized, wherein reactive metal becomes sulphided state from oxidation state.Concrete operations are in reactor, and 200 ℃ of following constant temperature 5 hours, 320 ℃ of following constant temperature 10 hours, the hydrogen volume air speed was 1000h with the hydrogen of sulfide hydrogen 0.8% (V)
-1, pressure is 5MPa.Hydrocracking catalyst HC-CAT7 reduces, the concrete operations condition for not hydrogen sulfide containing hydrogen 200 ℃ of following constant temperature 5 hours, 320 ℃ of following constant temperature 10 hours, the hydrogen volume air speed was 1000h
-1, pressure is 5MPa.
The character of table 4 embodiment 5～8 operational conditions and products obtained therefrom
Annotate: temperature of reaction refers to average reaction temperature among the embodiment.
As can be seen, when adopting the catalyzer of the modified beta zeolite with suitable granularity and multiple pore structure, diesel yield is higher from table 3 and table 4, and total liquid yield is higher.
Below described embodiment of the present invention in detail, can do a lot of improvement and variation obviously for a person skilled in the art and can not deviate from essence spirit of the present invention.All these changes and improvements are all within protection scope of the present invention.
Claims (10)
1. method of producing diesel oil and industrial chemicals by f-t synthetic wax, this method is included under the hydrocracking condition, the f-t synthetic wax raw material is contacted with the hydrogen hydrocracking catalyst, then the hydrocracking reaction product is carried out fractionation, the naphtha fraction that obtains, diesel oil distillate and boiling range are higher than the tail oil cut of diesel oil.
2. according to the described production method of claim 1, wherein said f-t synthetic wax is a cut heavier in the liquid product that obtains in the fischer-tropsch building-up process, is generally to contain C
19 +The molecule of hydro carbons.
3. according to the described production method of claim 1, wherein said tail oil cut can loop back the hydrocracking operation whole or in part.
4. according to any described production method of claim 1-3, the cut point of wherein said petroleum naphtha and diesel oil is 120～260 ℃, and the cut point of diesel oil and tail oil is 330～385 ℃.
5. according to any described production method of claim 1-3, the operational condition of wherein said hydrocracking is 3～20MPa for the hydrogen dividing potential drop, and temperature is 300～450 ℃, and volume space velocity is 0.1～20h during liquid
-1, hydrogen to oil volume ratio is 200～3000, and preferred, the operational condition of wherein said hydrocracking is: the hydrogen dividing potential drop is 5～15MPa, and temperature is 320～430 ℃, and volume space velocity is 0.2～10h during liquid
-1, hydrogen to oil volume ratio is 400～2000.
6. according to any described production method of claim 1-3, wherein said hydrocracking catalyst contains metal hydrogenation component, acid cracking component and carrier; Gross weight in catalyzer, described metal hydrogenation component is in its oxide form, its weight content in catalyzer is 0.1%～40%, and the weight content of acid cracking component in catalyzer is 0.5%～60%, and the weight content of carrier in catalyzer is 10%～80%.
7. according to the described production method of claim 6, the metal hydrogenation component in the wherein said hydrocracking catalyst is selected from one or more in group vib and/or the VIII family base metal; Preferably, wherein said group vib base metal is W and/or Mo, and VIII family base metal is Co and/or Ni; Preferred, in the gross weight of catalyzer, described base metal is 10%～30% in the weight content of oxide compound in catalyzer; Metal hydrogenation component in the perhaps wherein said hydrocracking catalyst is one or more in the VIII family precious metal; Preferred VIII family precious metal is Pt and/or Pd; And wherein in the gross weight of catalyzer, described VIII family precious metal is 0.2%～2% in the weight content of element in catalyzer.
8. according to the described production method of claim 6, wherein in the gross weight of catalyzer, the weight content of described acid cracking component in catalyzer is preferably 2%～30%, and preferred, the acid cracking component in the described hydrocracking catalyst is the β zeolite.
9. according to the described production method of claim 8, wherein said β zeolite as acid cracking component has following characteristic: SiO
2/ Al
2O
3Mol ratio is 20～150, and mean particle size is 0.1-0.5 μ m, specific surface 500-750m
2/ g, infrared acidity is 0.1～0.5mmol/g, Na
2O≤0.2w%, pore volume are 0.35-0.50ml/g; Preferred β zeolite has following characteristic: the aperture be the hole of 0.1～1.7nm account for total pore volume 20%～50%, the aperture accounts for 5%～20% of total pore volume for the hole of＞1.7～6.0nm, the aperture be the hole of 10.0～90.0nm account for total pore volume 30%～60%; Preferred β zeolite has following characteristic: SiO
2/ Al
2O
3Mol ratio is at 80-120, Na
2O≤0.15w%.
10. according to the described production method of claim 6, wherein in the gross weight of catalyzer, the weight content of described carrier in catalyzer is 15%～60%, preferably, wherein said carrier is selected from one or more in amorphous aluminum silicide, aluminum oxide, silicon oxide, clay and the Y zeolite.
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| CNA2007100901243A CN101177619A (en) | 2007-04-13 | 2007-04-13 | Method for producing diesel oil and chemical materials by f-t synthetic wax |
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| CNA2007100901243A CN101177619A (en) | 2007-04-13 | 2007-04-13 | Method for producing diesel oil and chemical materials by f-t synthetic wax |
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