CN104998668A - Catalyst for hydrogenated production of diesel oil with high cetane number by plant oil and preparation and usage methods of catalyst - Google Patents

Abstract

The invention discloses a catalyst for hydrogenated production of diesel oil with a high cetane number by plant oil and preparation and usage methods of the catalyst. According to the catalyst, a composite of a molecular sieve and activated aluminium oxide is taken as a carrier, traditional metals such as Ni, Mo, W and the like are taken as active components, and a phosphorous compound is taken as an auxiliary. The catalyst prepared by the method is suitable for preparing bio-diesel oil from palm oil, caster oil, soybean oil, sunflower oil, peanut oil, rapeseed oil, olive oil, sunflower oil or waste plant oil through a hydrogenation method, and is high in hydrodeoxygenation and isomeric selectivity. The prepared diesel oil product has the characteristics of being high in cetane number and low in viscosity and condensation point.

Description

One vegetable oil hydrogenation produces catalyst and the preparation using method thereof of high cetane number diesel oil

Technical field

The present invention relates to oil hydrogenation and prepare biodiesel catalysis technical field, particularly a kind of vegetable oil hydrogenation that is used for produces high cetane number diesel catalytic converter.That phosphorus-containing compound is the catalyst of auxiliary agent with molecular sieve-activated alumina for carrier is prepared with transition metal such as Ni, Mo, W for active component in particular.

Background technology

Biodiesel is the Novel clean-fuel in order to diesel oil substitute utilizing animal and plant fat etc. to produce.First generation biodiesel mainly fatty acid ester of low-carbon alcohol, based on methyl esters.Compared with petrifaction diesel, major advantage is: good combustibility; Sulfur content is low; Flash-point is high, uses safer; Raw material is renewable, but also exposes certain problem in use procedure: saturate methyl esters, easily separates out and block conveyance conduit in the season of cold; The cottonseed oil that saturation degree is low, rapeseed methylester, easy oxidation deterioration, not easily stores.Generate with deep hydrogenation the grease processing technology that aliphatic hydrocarbon is core and open up the new technology of producing liquid hydrocarbon fuel, i.e. second generation bio-fuel technology.Second generation biodiesel main component is liquid fat hydrocarbon; closer to petrifaction diesel in stuctures and properties; processing and use are all convenient than methyl esters class A fuel A; raw material not only can use rapeseed oil, cottonseed oil; also can use palm oil, soybean oil, animal tallow etc., method of hydrotreating prepares the method that biodiesel is considered to the biodiesel large-scale production of most potentiality.

Oil is industrial development " blood ".Along with expanding economy, various oil product, especially the demand of automotive fuel increases year by year, require that world's crude oil production amount and petroleum refining capacity improve year by year, but oil is non-renewable resources, Suitable development limited time.Coal is also the important sources of the energy, and the Suitable development time is longer compared with oil, but still limited amount, and be equally also non-renewable resources.Due to the exploitation quantitative limitation of petroleum resources year and other political factor, crude oil price Continued, and drive the price of primary energy to go up together, the energy new to exploitation like this, especially green regenerative energy sources provides opportunity.

Vegetable and animals oils, fat are regenerative resources, and their composition is mainly carbon, hydrogen and oxygen, and exist with the form of the glyceride form of saturated or unrighted acid or a small amount of free fatty.If automotive fuel just can be produced Molecular Cloning greatly in animal and plant fat for after Small molecular, provide the new forms of energy source producing clean fuel.Vegetable and animals oils, fat react having under hydrogen and catalyst existent condition, deoxygenation can be realized, also corresponding achieve Molecular Cloning greatly for micromolecular object, alkane derivative is generated after chain rupture, and these alkane major parts of producing are in diesel oil distillate scope, feature is that density is low, Cetane number is high, almost without sulphur.But the product after vegetable and animals oils, fat hydrogenation deoxidation is nearly all n-alkane, and condensation point is high, cannot directly as vehicle fuel.And vegetable and animals oils, fat have a large amount of water to generate in hydrogenation deoxidation process, conventional catalyst and technological process cannot meet long period and steadily produce.

Clear gusoline produces the development and application depending on hydrogen addition technology.Produce for clean diesel, though existing a lot of technology is available, oil refining enterprise still wishes that the hydrogenation new technology that renewal can be had more flexible and efficient occurs, thus more economically can produce clean diesel more neatly, meets the market demand of constantly change.

In catalytic carrier optimization, as US4510029, US4519951 disclose respectively with α-Al ₂o ₃with γ-Al ₂o ₃for the Ni-Al of carrier ₂o ₃catalyst.These patents have done some work be highly profitable in selection novel carriers.

In the improvement of active constituent, as Chinese patent bulletin 85103783 discloses the catalyst that a kind of Ni-Pd is active constituent, this catalyst has higher activity, but financial cost limits its commercial Application.

Patent CN 102989462 discloses a kind of method for making of high-activity fat hydrogenation catalyst.Using titanium dioxide-aluminum oxide as complex carrier, nickel is as active component, alkaline-earth metal is as auxiliary agent, first the method adopts coprecipitation method Kaolinite Preparation of Catalyst support precursor, catalyst precursor reduction and solidification granulating and forming, making final is active component, a certain amount of auxiliary agent of load with nickel, and titanium dioxide-aluminum oxide is the oil hydrogenation catalyst of carrier.This catalyst is lower to palm oil hydrogenated products iodine number, but catalyst preparation process is relatively loaded down with trivial details, and for carry out analytic explanation to other physical indexs of hydrogenated products.

Patent CN 1944610 discloses a kind of preparation method of consaturated oil hydrogenation catalyst, the method just cooking-pot type method preparation of simultaneously adding of the mixed solution of alkaline precipitating agent, water soluble nickel salt, molysite, alumina support, the precipitation method and infusion process combine by the method, Kaolinite Preparation of Catalyst granularity is less than 100 orders, there is higher specific area, be suitable for pore structure and the pore-size distribution of oil hydrogenation reaction, make catalyst have good activity and selectivity.But the hydrotreated lube base oil that the effect of this catalyst is only limitted to double bond in grease produces hydrogenated oil and fat.

Patent CN 102464998 discloses a kind of method that animal and plant fat catalytic hydrogenation produces fine-quality diesel oil.Animal and plant fat carries out hydrogenation deoxidation and olefin saturation in the presence of hydrogen and a catalyst, hydrogenation reaction effluent gas-liquid separation, liquid phase obtains gas, diesel oil distillate through fractionation and does not transform cut completely, and gained does not transform cut completely and loops back hydrogenation and finally obtain gas products, naphtha and diesel oil distillate.In the method, hydrogenation catalyst comprises Hydrobon catalyst and catalyst for hydro-upgrading, but it is poor that this catalyst is used for animal and plant fat hydrogenation selectivity, there is polarization in product, have gas products to reduce liquid product yield, and the boiling point not transforming cut is completely greater than 330 DEG C, in addition the boiling range of diesel oil distillate is 200 DEG C ~ 330 DEG C, diesel oil initial boiling point is high, and Cetane number is low, below 30, do not meet GB is greater than 45 requirement to diesel cetane-number.

A kind of method that EP1741768 relates to animal and plant fat hydrotreatment, the process route of isomery produces vegetable oil, directly can process the diesel product of high-quality by animal and plant fat.But there is certain restriction to raw material, require to add a certain proportion of diluent in the feed, require the sulfur content containing 50 ~ 20000ppm in raw material.The greatest problem that this technology exists is that the water that generates after have ignored hydrofinishing is to the serious adverse effect containing molecular sieve catalyst.

The technology such as the Hydrobrass of US Patent No. 20060186020, European patent EP 1693432 and Brazil are all on Diesel Oil Hydrofining Unit, carry out vegetable oil to mix refining, in order to improve the character of diesel product, do not relate to the exploitation of specific aim vegetable fat hydrogenation catalyst and the foundation of independent process technology.

Summary of the invention

The object of the invention is the deficiency for existing vegetable fat hydrogenation catalyst development technique, provide a kind of animal and plant fat hydrogenation to produce high cetane number diesel catalytic and preparation method thereof.The method takes extruded moulding and incipient impregnation method to prepare hydrogenation catalyst; be conducive to the scale preparation of catalyst, and catalyst has selective hydrogenation deoxidation and appropriate isomerization feature, diesel yield is high; Cetane number is high, and has the feature of low viscosity, low condensation point.

The present invention one vegetable oil hydrogenation produces the Catalysts and its preparation method of high cetane number diesel oil, it is characterized in that:

Catalyst activity component is one or more of Ni, Mo, W, containing P auxiliary agent from phosphoric acid, aluminium dihydrogen phosphate, one or more in sodium hypophosphite, calcium dihydrogen phosphate, magnesium dihydrogen phosphate, active metal composition is with metal oxide mass percentage, its ratio is 2.0 ~ 15.0wt%NiO, 2.0 ~ 15.0wt%MoO ₃, 10.0 ~ 30.0wt%NiO, auxiliary agent content is 0.5 ~ 15.0wt%, and surplus is catalyst carrier.Catalyst carrier is the composite carrier of activated alumina and molecular sieve, molecular sieve is one or more in ZSM-5, ZSM-22, HY, USY, MCM-41, SAPO-231, its ratio is 5.0 ~ 20.0wt% of catalyst carrier quality, and surplus is activated alumina.

Catalyst preparing concrete steps are:

(1) carrier Constitutive active aluminium oxide mixes with phosphorus-containing compound with the complex carrier of molecular sieve, kneading, extruded moulding, 60 ~ 120 DEG C of drying 5 ~ 12h, and 300 ~ 550 DEG C of roasting 1 ~ 8h, cool for subsequent use;

(2) to be 5 ~ 30wt% by the mass concentration prepared be impregnated on the carrier (1) prepared containing the aqueous metal salt of Ni, Mo and/or W in ultrasonic immersing, dipping adopts equal-volume ultrasonic immersing method, temperature is 40 ~ 90 DEG C, ultrasonic power is 50KHz, time is 2 ~ 10h, then 8 ~ 12h, roasting 1 ~ 8h under air atmosphere in the Muffle furnace of 300 ~ 600 DEG C is dried for 80 ~ 150 DEG C;

(3) In-situ sulphiding catalyst uses in front device In-situ sulphiding, and vulcanizing agent is the one in dimethyl disulfide, carbon disulfide, and sulfurized oil is the one of n-hexane, aviation kerosine, naphtha, and vulcanizing agent concentration is 0.5 ~ 5.0wt%.

Detailed description of the invention

Following non-limitative example is for illustration of various embodiments of the present invention.

Embodiment 1:(1) take activated alumina 354.0g, concentration is the phosphate dihydrogen aluminum solution 342.0g of 10%, and above material is mixed rear extrusion, 120 DEG C of dried overnight, and it is for subsequent use that carrier is made in 550 DEG C of roastings; (2) ammonium metatungstate 116.3g is taken, Nickelous nitrate hexahydrate 97.4g, be made into the metal salt solution that concentration is 10% respectively, on the carrier adopting equal-volume ultrasonic immersing method to be impregnated into by metal salt solution (1) to prepare, flood 60 DEG C, the time is 4h, dries 12h for 120 DEG C, the roasting 6h of 450 DEG C, makes catalyst W-Ni-P/ γ-Al ₂o ₃, catalyst activity component forms about 20%WO ₃, 5%NiO, 2%P, surplus is carrier.

Embodiment 2:(1) take activated alumina 354.0g, concentration is the phosphate dihydrogen aluminum solution 342.0g of 10%, and above material is mixed rear extrusion, 120 DEG C of dried overnight, and it is for subsequent use that carrier is made in 550 DEG C of roastings; (2) ammonium metatungstate 116.3g is taken, four water ammonium molybdate 30.7g, be made into the metal salt solution that concentration is 10% respectively, on the carrier adopting equal-volume ultrasonic immersing method to be impregnated into by metal salt solution (1) to prepare, flood 60 DEG C, the time is 4h, dries 12h for 120 DEG C, the roasting 6h of 450 DEG C, makes catalyst W-Mo-P/ γ-Al ₂o ₃, catalyst composition is containing about 20%WO ₃, 5%MoO ₃, 2%P.

Embodiment 3:(1) take activated alumina 354.0g, concentration is the phosphate dihydrogen aluminum solution 342.0g of 10%, and above material is mixed rear extrusion, 120 DEG C of dried overnight, and it is for subsequent use that carrier is made in 550 DEG C of roastings; (2) Nickelous nitrate hexahydrate 389.6g is taken, four water ammonium molybdate 30.7g, be made into the metal salt solution that concentration is 10% respectively, on the carrier adopting equal-volume ultrasonic immersing method to be impregnated into by metal salt solution (1) to prepare, dipping temperature 60 DEG C, the time is 4h, dries 12h for 120 DEG C, the roasting 6h of 450 DEG C, makes catalyst n i-Mo-P/ γ-Al ₂o ₃, catalyst composition contains about 20%NiO, 5%MoO ₃, 2%P.

Embodiment 4:(1) take activated alumina 336.3g, ZSM-5 molecular sieve 17.7g, concentration is the phosphate dihydrogen aluminum solution 342.0g of 10%, and above material is mixed rear extrusion, 120 DEG C of dried overnight, and it is for subsequent use that carrier is made in 550 DEG C of roastings; (2) ammonium metatungstate 87.3g is taken, Ammonium Molybdate Tetrahydrate 30.7g, Nickelous nitrate hexahydrate 97.4g, be made into the metal salt solution that concentration is 10% respectively, on the carrier adopting equal-volume ultrasonic immersing method to be impregnated into by metal salt solution (1) to prepare, dipping temperature 60 DEG C, time is 6h, dry 12h, the roasting 8h of 550 DEG C, make catalyst W-Mo-Ni-P/ γ-Al for 120 DEG C ₂o ₃-ZSM-5, catalyst composition is containing about 15%WO ₃, 5%MoO ₃, 5%NiO, 2%P, ZSM-5 account for carrier composition 5%.

Embodiment 5:(1) take activated alumina 328.5g, USY molecular sieve 36.5g, concentration is the phosphoric acid solution 316.0g of 10%, and above material is mixed rear extrusion, 120 DEG C of dried overnight, and it is for subsequent use that carrier is made in 550 DEG C of roastings; (2) ammonium metatungstate 87.3g is taken, Ammonium Molybdate Tetrahydrate 30.7g, Nickelous nitrate hexahydrate 97.4g, be made into the metal salt solution that concentration is 10% respectively, on the carrier adopting equal-volume ultrasonic immersing method to be impregnated into by metal salt solution (1) to prepare, dipping temperature 60 DEG C, time is 6h, dry 12h, the roasting 8h of 550 DEG C, make catalyst W-Mo-Ni-P/ γ-Al for 120 DEG C ₂o ₃-ZSM-5, catalyst composition is containing about 15%WO ₃, 5%MoO ₃, 5%NiO, 2%P, USY account for carrier composition 10%.

Embodiment 6:(1) take activated alumina 284.8g, MCM-41 molecular sieve 71.2g, concentration is the biphosphate calcium solution 377.5g of 10%, and above material is mixed rear extrusion, 120 DEG C of dried overnight, and it is for subsequent use that carrier is made in 550 DEG C of roastings; (2) ammonium metatungstate 87.3g is taken, Ammonium Molybdate Tetrahydrate 30.7g, Nickelous nitrate hexahydrate 97.4g, be made into the metal salt solution that concentration is 10% respectively, on the carrier adopting equal-volume ultrasonic immersing method to be impregnated into by metal salt solution (1) to prepare, dipping temperature 60 DEG C, time is 6h, dry 12h, the roasting 8h of 550 DEG C, make catalyst W-Mo-Ni-P/ γ-Al for 120 DEG C ₂o ₃-ZSM-5, catalyst composition is containing about 15%WO ₃, 5%MoO ₃, 5%NiO, 2%P, MCM-41 account for carrier composition 10%.

The catalyst of high cetane number diesel oil is produced in vegetable oil hydrogenation deoxidation prepared by the present invention and isomerization, by the catalyst of the present invention that above-described embodiment is obtained, fixed bed reactors carry out activity rating, experiment proves under relatively mild reaction conditions (volume space velocity 1.0h when temperature 360 DEG C, Hydrogen Vapor Pressure 6MPa, liquid ^-1, hydrogen-oil ratio is 1000:1), conversion ratio can close to 100%, and diesel yield is higher than 90%, and Cetane number is greater than 60.Detailed Experimental data are as follows:

Experiment 1: palm oil Hydrogenation is tested for diesel oil

Carry out hydro-conversion experiment to palm oil, catalyst in-situ presulfurization with catalyst prepared by embodiment 1, vulcanizing agent is dimethyl disulfide (concentration 2wt%, sulfurized oil is aviation kerosine), conditions of vulcanization temperature 290 DEG C, Hydrogen Vapor Pressure 7MPa, volume space velocity 1.0h during liquid ^-1be 1000:1 with hydrogen-oil ratio, cure time 12h, Detailed Experimental data list in table 1.

Table 1 palm oil Hydrogenation Experiment data

	Charging	Diesel component
			Yield (%)	——	90.4
Density (g/cm 3)	0.9340	0.7881
			Viscosity (mPas)	4.672	3.443
O(wt％)	5.74	0.02
			N-C9 ~ n-C14 yield (%)	——	3.01
N-C15 yield (%)	——	12.41
			N-C16 yield (%)	——	24.28
N-C17 yield (%)	——	17.26
			N-C18 yield (%)	——	31.72
N-C19 ~ n-C23 yield (%)	——	1.14
			I-C9 ~ i-C23 yield (%)	——	7.21
Cetane number	35	68
			Condensation point (DEG C)	3.5	-5

Experiment 2: palm oil Hydrogenation is tested for diesel oil

Carry out hydro-conversion experiment to palm oil, catalyst in-situ presulfurization with catalyst prepared by embodiment 4, vulcanizing agent is dimethyl disulfide (concentration 2wt%, sulfurized oil is aviation kerosine), conditions of vulcanization temperature 290 DEG C, Hydrogen Vapor Pressure 7MPa, volume space velocity 1.0h during liquid ^-1be 1000:1 with hydrogen-oil ratio, cure time 12h, Detailed Experimental data list in table 2.

Table 2 palm oil Hydrogenation Experiment data

	Charging	Diesel component
			Yield (%)	——	92.5
Density (g/cm 3)	0.9340	0.7875
			Viscosity (mPas)	4.672	3.542
O(wt％)	5.74	0.01
			N-C9 ~ n-C14 yield (%)	——	6.00
N-C15 yield (%)	——	15.19
			N-C16 yield (%)	——	20.5

N-C17 yield (%)	——	21.05
			N-C18 yield (%)	——	26.13
N-C19 ~ n-C23 yield (%)	——	4.09
			I-C9 ~ i-C14 yield (%)	——	5.93
Cetane number	35	66
			Condensation point (DEG C)	3.5	-14

Experiment 3: waste oil Hydrogenation is tested for diesel oil

Carry out hydro-conversion experiment to waste oil, catalyst in-situ presulfurization with catalyst prepared by embodiment 5, vulcanizing agent is dimethyl disulfide (concentration 2wt%, sulfurized oil is aviation kerosine), conditions of vulcanization temperature 290 DEG C, Hydrogen Vapor Pressure 7MPa, volume space velocity 1.0h during liquid ^-1be 1000:1 with hydrogen-oil ratio, cure time 12h, Detailed Experimental data are listed in table 2 Detailed Experimental data and are listed in table 3.

Table 3 waste oil Hydrogenation Experiment data

	Charging	Diesel component
			Yield (%)	——	88.3
Density (g/cm 3)	0.9505	0.8085
			Viscosity (mPas)	5.214	4.056
O(wt％)	6.02	0.04
			N-C9 ~ n-C14 yield (%)	——	2.77
N-C15 yield (%)	——	7.89
			N-C16 yield (%)	——	26.67
N-C17 yield (%)	——	16.31
			N-C18 yield (%)	——	34.41
N-C19 ~ n-C23 yield (%)	——	2.55
			I-C9 ~ i-C14 yield (%)	——	7.02
Cetane number	——	60.8
			Condensation point (DEG C)	——	-10

As can be seen from above-mentioned experimental result, under catalyst action of the present invention, diesel oil distillate (180 ~ 360 DEG C) yield is more than 85%,, O hetero atom removal efficiency is greater than 99%, C15-C18 n-alkane proportion in diesel oil composition is maximum, isomerization rate is between 6 ~ 7%, and this is also the main cause that diesel product has high cetane number and low condensation point simultaneously.

Claims (6)

1. a vegetable oil hydrogenation produces catalyst and the preparation using method thereof of high cetane number diesel oil, it is characterized in that this catalyst activity component is one or more of Ni, Mo, W, auxiliary agent is phosphorus-containing compound, catalyst carrier is the composite carrier of activated alumina and molecular sieve, active metal composition is with metal oxide mass percentage, its ratio is 2.0 ~ 15.0wt%NiO, 2.0 ~ 15.0wt%MoO ₃, 10.0 ~ 30.0wt%WO ₃, auxiliary agent content is 0.5 ~ 15.0wt%, and surplus is catalyst carrier.

2. catalyst according to claim 1, is characterized in that auxiliary agent phosphorus-containing compound is phosphoric acid, aluminium dihydrogen phosphate, one or more in sodium hypophosphite, calcium dihydrogen phosphate, magnesium dihydrogen phosphate.

3. catalyst according to claim 1, it is characterized in that catalyst carrier is the composite carrier of activated alumina and molecular sieve, molecular sieve is one or more in ZSM-5, ZSM-22, HY, USY, MCM-41, SAPO-231, its ratio is 5.0 ~ 20.0wt% of catalyst carrier quality, and surplus is activated alumina.

4. utilize the catalyst vegetable oil hydrogenation described in claim 1 to produce the method for diesel oil, it is characterized in that the vegetable oil raw materials producing diesel oil for hydrogenation catalyst is palm oil, castor oil, soybean oil, sunflower oil, peanut oil, rapeseed oil, olive oil, sunflower oil or waste vegetable oil fat, catalytic reaction is mainly hydrogenation deoxidation and isomerization reaction.

5. method according to claim 4, it is characterized in that the method produces product is high cetane number diesel oil distillate, and Cetane number is greater than 60, and yield is greater than 90%.

6. the preparation method of catalyst according to claim 1, is characterized in that, comprise the steps:

(1) carrier Constitutive active aluminium oxide mixes with phosphorus-containing compound with the complex carrier of molecular sieve, kneading, extruded moulding, 60 ~ 120 DEG C of drying 5 ~ 12h, and 300 ~ 550 DEG C of roasting 1 ~ 8h, cool for subsequent use;

(2) ultrasonic immersing be 5 ~ 30wt% by the mass concentration prepared containing Ni, Mo and or the aqueous metal salt liquid of W be impregnated on the carrier (1) prepared, dipping adopts equal-volume ultrasonic immersing method, temperature is 40 ~ 90 DEG C, ultrasonic power is 50KHz, time is 2 ~ 10h, then 8 ~ 12h, roasting 1 ~ 8h under air atmosphere in the Muffle furnace of 300 ~ 600 DEG C is dried for 80 ~ 150 DEG C;

(3) In-situ sulphiding catalyst uses in front device In-situ sulphiding, and vulcanizing agent is the one in dimethyl disulfide, carbon disulfide, and sulfurized oil is the one of n-hexane, aviation kerosine, naphtha, and vulcanizing agent concentration is 0.5 ~ 5.0wt%.