CN1227337C - Catalyst for hydrogenation upgrading heavy and residual oil and application thereof - Google Patents

Abstract

The present invention discloses a novel catalyst for hydroupgrading heavy oil and residual oil. The hydrocatalyst of the present invention is an oil solution colloid containing Mo and W, wherein the average grain size of Mo and W is less than 500 nanometers. The catalyst can be widely used for a hydroreaction technology, a hydrocracking technology, etc. for the heavy oil and the residual oil. In these technologies, the catalyst containing Mo and W is in general uniformly dispersed in the heavy oil and the residual oil at first and inferior heavy oil and inferior residual oil containing the catalyst make a hydroreaction with hydrogen so as to enhance the hydroreaction efficiency of the heavy oil and the residual oil on the premise of low catalyst cost.

Description

Catalyst for hydrogenation upgrading heavy and residual oil and application thereof

1, technical field

The present invention relates to a kind of heavy, residual oil hydrocatalyst and preparation method thereof, particularly dreg-oil suspension bed hydrogenation cracking catalyzer.

2, background technology

The molybdenum ore of China and the reserves of tungsten ore all are positioned at prostatitis, the world, and abundant Mineral resources are China's development molybdenum ore and tungsten ore processing, widely popularize the application of molybdenum, tungsten, and very advantageous conditions and solid basis are provided.Molybdenum and tungsten are widely used in fields such as metallurgy, Aeronautics and Astronautics, chemical industry, petrochemical industry, biological medicine and mechanical workout, wherein have only few part to be used for petrochemical field, and they also almost are as the hydrogenation catalyst in the oil refining process in the application of petrochemical field entirely.At present, the heavy and poor qualityization along with the continuous change of crude oil extraction, the hydrogen addition technology of each refinery's counterweight, residual oil is more and more paid close attention to, and the hydrogenation activity of molybdenum and tungsten is on record, and because many technical reasons are restricted their application.The fixed bed hydrogenation technical development time is longer, and technology is comparative maturity also, and use range is also wider.The hydrogenation catalyst that is used for fixing bed normally is supported on the solid catalyst of the metals such as molybdenum, nickel, cobalt, tungsten and iron on the carrier, because the fixed bed hydrogenation technology is to the having relatively high expectations of raw material, so its application has been subjected to certain restriction.And the suspension bed residual oil hydrogenation technology is stronger to the adaptability of raw material, can process various inferior raw materials.The catalyzer that is used for suspension bed residual oil hydrogenation technology mainly contains three kinds, is respectively: solid powder th-1 catalyst, water-soluble catalyst, oil-soluble catalyst.Solid powder th-1 catalyst and the water-soluble catalyst dispersion effect in oil is relatively poor, these catalyzer generally the median size in oil more than 10 μ m, so the hydrogenation effect is relatively poor.Though and the oil-soluble catalyst dispersion effect is fine, preparation is complicated and cost an arm and a leg, even the toxicity that has is very big, is unsuitable for industrial application.A large amount of on the other hand MoS ₂And WS ₂As the lubricant of mechanical workout, in these lubricants, MoS ₂And WS ₂Particle diameter can be worked into below 500 nanometers, thinner reach tens nanometers, bibliographical information has been arranged now, can process the MoS of several nanometers ₂And WS ₂If, with these MoS ₂And WS ₂Nano material introduce the oil refining field as hydrogenation catalyst, will bring huge development to petrochemical industry.

Cooperate with molybdenum naphthenate and cobalt naphthenate in the United States Patent (USP) 4285804, and will be rich in the tail oil circulation of metal.For example work as fresh feed and contain Mo 70 μ g/g, Co 20 μ g/g, per hour advance 6.3L, and the circulation tail oil contains Mo1930 μ g/g, Co 570 μ g/g per hour advance 0.7L, and fresh feed is mixed into reactor at furnace outlet and circulation tail oil, the asphaltene removal that subtracts slag can reach 70-80m%, and 550 ℃+productive rate can reach 35～47m%.

United States Patent (USP) 4227642 and 4134825 is dissolved in naphthenic acid or resin hydrochlorate in a part of oil, enter reactor then, as: with molybdenum naphthenate 350 μ g/g (in metal), at 438 ℃, 17.1MPa following hydrogenation, the desulfurization degree of the normal slag of cold air lake is 50m%, and demetallization per is 91m%, and the green coke amount has only 0.4m%.

United States Patent (USP) 4125455 is used C _7-12Lipid acid molybdenum or tungsten be dissolved in the residual oil raw material, add-on is counted 500～1000 μ g/g with metal.At 430 ℃, hydrogenation reaction under the 13.7MPa condition.When making catalyzer with molybdenum caprylate, the metal add-on be 590 μ g/g reaction after 8 hours 454 ℃+transformation efficiency can reach 80m%.

Many carbonyl compound prepared in reaction catalyzer of the sulfide of United States Patent (USP) 4839326 usefulness molybdenums and tungsten and iron, cobalt, nickel, for example: aluminum oxide is placed on (NH ₄) ₆Mo ₇O ₂₄Soak in the aqueous solution, then with the 400 ℃ of roastings in containing the air of hydrogen sulfide of wetted aluminum oxide, and then under the protection of tetrahydrofuran (THF) with Co ₂(CO) ₈Reaction is made and is contained Mo 4.97m%, the catalyzer of Co 1.94m%, and be that raw material carries out hydrogenation reaction on autoclave with the catalytic cycle oil, reaction conditions is 325 ℃, 3.15MPa, air speed 1.0, stir speed (S.S.) 1500rpm.Obtain desulfurization degree 60m%, the result of denitrification percent 10m%.

In the method that above-mentioned patent is mentioned, though the dispersion effect of many catalyzer is fine, but still there are some shortcomings, as: the Preparation of Catalyst more complicated, and poisonous, harmful, bigger to human body harm.The catalyzer add-on is also very big in addition, and this makes the catalyzer cost higher, can't reach the purpose of industrial application.

In the article of the 23rd volume fourth phase " development of molybdenumdisulphide finish " in " China molybdenum industry " August in 1999, mention molybdenumdisulphide powder and a certain proportion of wetting agent and dispersant, mixture is stirred at 40 ℃～80 ℃, adding machine oil then stirs fast and obtains uniform finish, molybdenumdisulphide accounts for 23m% in the finish, and it is used as lubricant.

In the above-mentioned method of mentioning, the preparation method of molybdenumdisulphide finish is fairly simple, but if with this finish as hydrogenation catalyst, probably effect can be very not desirable, because the median size of the molybdenumdisulphide that obtains in this way about 1 micron, is difficult to the state that reaches more tiny.

3, summary of the invention

The objective of the invention is to find a kind of suitable hydrogenation catalyst, make median size that this catalyzer distributes in oil below 500nm.This hydrogenation catalyst can obtain higher hydrogenation conversion when processing inferior heavy, residual oil.Another object of the present invention provides a kind of preparation method of heavy, residual oil hydrocatalyst, to simplify the cost that preparation process reduces catalyzer.

The invention provides the hydrogenation catalyst that uses in a kind of heavy, residual hydrogenation process, this catalyzer is the finish colloid that contains reactive metal molybdenum and/or tungsten, and wherein the median size of Mo, W is below 500nm, and the content of reactive metal is between 1～20m%.

Also contain dispersion agent in the catalyzer, comprise tensio-active agents such as tween, class of department, OP, Fatty Alcohol(C12-C14 and C12-C18) and alicyclic organic, the content in catalyzer is 0.1～10.0m%, is preferably 0.5～2.0m%;

Can also contain stablizer in the catalyzer in addition, comprise long chain alkane, naphthenic hydrocarbon, polycyclic aromatic hydrocarbons and derivative thereof and various wax, as: heptane, furans, thiophene, quinoline, beeswax and paraffin etc., its content in catalyzer is 0.1～10.0m%, is preferably 0.5～2.0m%;

Used solvent can be 100 ℃～500 ℃ any one intermediates in the refinery in the preparation catalyzer process, as among various lubricating oil, machine oil, wax oil, gasoline, diesel oil, kerosene and/or the VGO one or more.

Preparation of catalysts method of the present invention is: require MoS according to catalyst content ₂And/or WS ₂Powder mixes with solvent phase and places reaction vessel, and in mixture, add dispersion agent and stablizer, in the presence of hydrogen, stirred 2～8 hours in 60 ℃～100 ℃, and at 300 ℃～400 ℃, kept under the condition of pressure 5～15MPa 4～10 hours, and constantly stir, leave standstill and isolate throw out then at room temperature, promptly obtain the colloid finish of catalyzer.

Wherein related dispersion agent comprises tensio-active agents such as tween, class of department, OP, Fatty Alcohol(C12-C14 and C12-C18) and alicyclic organic, and the content in catalyzer is 1～10.0m%, is preferably 0.5～2.0m%; Stablizer comprises long chain alkane, naphthenic hydrocarbon, polycyclic aromatic hydrocarbons and derivative thereof and various wax, as: heptane, furans, thiophene, quinoline, beeswax and paraffin etc., its content in catalyzer is 0.1～10.0m%, is preferably 0.5～2.0m%; Solvent can be any one intermediates of 100 ℃～500 ℃ in the refinery, such as among various lubricating oil, machine oil, wax oil, gasoline, diesel oil, kerosene and/or the VGO one or more.The weight that the present invention relates in addition, residual oil can be the residual oil that crude distillation obtains, as long residuum, vacuum residuum, heavy-gravity heavy crude oil, and de-oiled asphalt, the also organism that obtains of oil sands bitumen, shale oil and the dry distillation of coal.

Above-mentioned MoS ₂And WS ₂Powder diameter is preferably in below 1 micron.

Wherein time of repose is generally at 15～45 days.

This catalyzer can be used for hydrocracking process of suspended bed, and catalyst levels is counted 50～5000 μ g/g with metal, generally at 50～500 μ g/g; For different material oil, operational condition is different, and the hydrogenator operational condition is usually: pressure 2～20MPa is preferably 8～14MPa; 300～470 ℃ of temperature are preferably 350～450 ℃; Liquid hourly space velocity 0.2～2.0h ^-1, be preferably 0.7～2.0h ^-1Hydrogen to oil volume ratio (under the standard pressure) 200～1200 is preferably 500～1000.

Advantage of the present invention is:

It is few that 1 catalyzer of the present invention has add-on, be generally≤400 μ g/g (in metal), active high, advantages such as good stability. adopt catalyzer of the present invention, to the high inferior heavy of sulphur, nitrogen, metal impurities content height and carbon residue, when residual oil carries out floating bed hydrocracking, can improve the yield of liquid product greatly, liquid product yield can reach more than the 80m%; When carrying out hydrogenation reaction, also have higher desulfurization degree, can reach more than the 60m% usually.

2 hydrogenation processes are used very a spot of hydrogenation catalyst, can not reclaim catalyzer, have saved high catalyst recovery expense.

3 in the hydrogenation process of weight, residual oil, and method for preparing catalyst of the present invention is simple, and cost is lower.

4, embodiment

Embodiment 1

With 25.2 gram MoS ₂Ultrafine powder and 205.5 gram vacuum pump machine oil add in the autoclave, each 1.0 gram of class 80 of adding department and OP7 add beeswax 3.0 grams again, and first hydrogen pressure is 4.5MPa, then temperature is risen to 70 ℃ of reactions after 3 hours, continue to heat up,, then hydrogen pressure is remained on 10.0MPa 240 ℃ and 320 ℃ of each isothermal reactions 1 hour, under the condition that temperature is 380 ℃, reacted 4 hours, in the reaction process otherwise stop stirring, stir speed (S.S.) should remain on 300 rev/mins.Reaction is reduced to room temperature with device after finishing, and reaction product is poured in the clean bottle, leaves standstill 30 days, and unreacted throw out is separated, and the uniform product liquid that obtains is the hydrogenation catalyst that contains molybdenum 5.74m%, code name C-1

Embodiment 2

With 20.5 gram MoS ₂Ultrafine powder and 210.0 gram VGO add in the autoclave, add each 1.0 gram of pure and mild hydroxyl methyl-formiate, add heptane 3.0 grams again, first hydrogen pressure is 4.5MPa, then temperature is risen to 80 ℃ of reactions after 3 hours, continue to heat up,, then hydrogen pressure is remained on 10.0MPa 240 ℃ and 320 ℃ of each isothermal reactions 1 hour, under the condition that temperature is 390 ℃, reacted 6 hours, in the reaction process otherwise stop stirring, stir speed (S.S.) should remain on 300 rev/mins.Reaction is reduced to room temperature with device after finishing, and reaction product is poured in the clean bottle, leaves standstill 20 days, and unreacted throw out is separated, and the uniform product liquid that obtains is the hydrogenation catalyst that contains molybdenum 4.80m%, code name C-2

Embodiment 3

With 27.7 gram WS ₂Ultrafine powder and 220.2 gram vacuum pump machine oil add in the autoclave, each 1.0 gram of class 80 of adding department and OP7 add beeswax 3.0 grams again, and first hydrogen pressure is 4.5MPa, then temperature is risen to 70 ℃ of reactions after 3 hours, continue to heat up,, then hydrogen pressure is remained on 10.0MPa 240 ℃ and 320 ℃ of each isothermal reactions 1 hour, under the condition that temperature is 385 ℃, reacted 5 hours, in the reaction process otherwise stop stirring, stir speed (S.S.) should remain on 300 rev/mins.Reaction is reduced to room temperature with device after finishing, and reaction product is poured in the clean bottle, leaves standstill 40 days, and unreacted throw out is separated, and the uniform product liquid that obtains is the hydrogenation catalyst that contains tungsten 6.96m%, code name C-3.

Embodiment 4

With 24.6 gram WS ₂Ultrafine powder and 198.3 gram VGO add in the autoclave, add each 1.0 gram of hexanol and hydroxyl methyl-formiate, add thionaphthene 3.0 grams again, first hydrogen pressure is 4.5MPa, then temperature is risen to 80 ℃ of reactions after 3 hours, continue to heat up,, then hydrogen pressure is remained on 10.0MPa 240 ℃ and 320 ℃ of each isothermal reactions 1 hour, under the condition that temperature is 390 ℃, reacted 6 hours, in the reaction process otherwise stop stirring, stir speed (S.S.) should remain on 300 rev/mins.Reaction is reduced to room temperature with device after finishing, and reaction product is poured in the clean bottle, leaves standstill 40 days, and unreacted throw out is separated, and the uniform product that obtains is the hydrogenation catalyst that contains tungsten 5.30m%, code name C-4.

Embodiment 5

Catalyzer C-1 and C-3 are obtained containing the catalyzer of molybdenum 2.87m%, tungsten 3.48m%, code name C-5 by 1: 1 mixed.

Embodiment 6

Catalyzer C-2 and C-4 are obtained containing the catalyzer of molybdenum 2.40m%, tungsten 2.65m%, code name C-6 by 1: 1 mixed.The composition and the median size of each catalyzer have been provided in the table 1.

Table 1 catalyzer is formed and character

Numbering	C-1	C-2	C-3	C-4	C-5	C-6
							Form m%
Metal content m%	5.74	4.80	6.96	5.30	6.35	5.05
							Solvent m%	92.09	93.03	91.02	92.45	91.55	92.74
Dispersion agent m%	0.87	0.87	0.81	0.90	0.84	0.88
							Stablizer m%	1.30	1.30	1.21	1.35	1.26	1.33
The metal median size *，nm	450	500	450	500	500	500

^*Here said metal median size adopts transmission electron microscope to record.Generally choosing bigger particle is standard.So real median size should be under this scope.

Example 7～12

The hydrocracking test that example 7～12 carries out on small-sized continuous apparatus for catalyzer of the present invention.Test raw material is to subtract slag in normal slag of isolated island and the sand, and test raw material character sees Table 2.The normal slag sulphur content of isolated island height as shown in Table 2, metal content is higher, and colloid, asphalt content are also higher, and carbon residue reaches 8.73m%, is a kind of more unmanageable poor residuum.And subtract slag sulphur, nitrogen content height in the sand, and metal content is also higher, and asphalt content reaches 8.4m%, and carbon residue reaches 20.73m%, also is a kind of more unmanageable poor residuum.

Table 2 floating bed hydrocracking stock oil character

Project	The normal slag of isolated island	Subtract slag in the sand
			Density kg/m 3(20℃)	965.3	1024.8
Carbon residue m%	8.73	20.73
			Ultimate analysis
C	84.78	83.52
			H	11.61	10.43
S	1.94	4.95
			N	0.1316	0.35
Metal analysis
			Fe	12.47	8.16
Ni	24.47	43.4
			V	4.91	143.6
Proximate analysis
			Saturated branch	31.4	9.9
Fragrance divides	30.6	52.2
			Colloid	36.6	29.5
Bituminous matter	1.6	8.4

Example 7～12 is being investigated on the small-sized continuous apparatus under operational conditions such as different pressures, temperature, air speed, catalyzer add-on, when using the catalyzer of different compositions, and the conversion of residual oil and the coke forming property of reaction process, test-results is listed in the table 3.The result listed by table 3 shows: hydrogenation catalyst of the present invention has active high advantage. adopt catalyzer of the present invention, to the high inferior heavy of sulphur, nitrogen, metal impurities content height and carbon residue, when residual oil carries out floating bed hydrocracking, can suppress green coke to greatest extent, under add-on≤400 μ g/g (in metal) conditions,＜500 ℃ of liquid product yields can reach more than the 80m%.

Table 3 hydrocracking test-results

Project	C-1	C-2	C-3	C-4	C-5	C-6
							Stock oil	Isolated island residual oil	Subtract slag in the sand	Isolated island residual oil	Subtract slag in the sand	Isolated island residual oil	Subtract slag in the sand
Catalytic amount μ g/g	300	250	250	250	300	300
							Reaction pressure MPa	10	14	8	12	10	14
Temperature of reaction ℃	435	440	437	438	435	440
							Hydrogen-oil ratio	800	1000	700	900	1000	1200
Air speed V/V	1.0	0.8	1.0	0.8	0.9	1.0
							Product distribution m%
＜180℃	10.2	12.1	10.7	11.6	11.8	13.3
							180-350℃	24.4.	34.6	27.4	33.5	28.2	35.0
350-500℃	45.8	34.3	44.6	34.4	44.5	34.2
							＞500℃	19.4	18.3	17.2	19.7	15.4	16.8
Coke	0.2	0.7	0.1	0.8	0.1	0.7

Embodiment 13～18

Hydrogenating desulfurization, denitrification test that embodiment 13～18 carries out on autoclave for catalyzer of the present invention.Test raw material is that isolated island subtracts slag and husky light normal slag (seeing Table 4).Isolated island subtracts slag sulphur content height as shown in Table 4, and metal content and colloid, asphalt content are also higher, and carbon residue reaches 14.68m%, is a kind of more unmanageable poor residuum.And husky light normal slag sulphur content height, metal content is also higher, and asphalt content reaches 3.2m%, and carbon residue reaches 9.71m%, also is a kind of more unmanageable poor residuum.

Table 4 autoclave hydrogenation reaction feedstock property

Project	Isolated island subtracts slag	Husky light normal slag
			Density (20 ℃) kg/m 3	983.5	969.4
Carbon residue m%	14.68	9.71
			Ultimate analysis m%
C	84.49	87.76
			H	11.15	11.38
S	2.62	3.38
			N	0.78	0.17
Metallic element μ g/g
			Fe	31.46	2.37
Ni	35.00	11.10
			V	5.07	37.50
Na	7.50	1.53
			Ca	22.00	1.25
Four proximate analysis m%
			Stable hydrocarbon	11.1	40.3
Aromatic hydrocarbon	36.3	42.2
			Colloid	50.3	14.3
Bituminous matter	2.3	3.2

Example 13～18 is being investigated on the autoclave under operational conditions such as different pressures, temperature, reaction times, catalyzer add-on, when using the catalyzer of different compositions, and the desulfurization degree of residual oil and denitrification percent, test-results is listed in the table 5.

Table 5 autoclave hydrogenation reaction test-results

Project	C-2	C-4	C-3	C-4	C-5	C-6
							Material name	Isolated island subtracts slag	Husky light normal slag	Isolated island subtracts slag	Husky light normal slag	Isolated island subtracts slag	Husky light normal slag
Catalytic amount μ g/g	250	250	250	300	300	300
							Reaction pressure MPa	14	10	12	14	12	14
Temperature of reaction ℃	395	385	380	390	385	385
							Reaction times h -1	5	4.5	4	3.5	4	4
Desulfurization degree m%	66.3	68.5	67.2	69.8	72.7	73.9
							Denitrification percent m%	45.6	47.1	42.8	44.4	47.5	48.0

Can find out that by table 5 result hydrogenation catalyst of the present invention has higher hydrogenation activity.Adopt catalyzer of the present invention, to the high inferior heavy of sulphur, nitrogen, metal impurities content height and carbon residue, when residual oil carries out hydrogenation reaction, adding under catalyzer add-on≤400 μ g/g (in metal) conditions, the desulfurization degree of residual oil surpasses 60m%, and denitrification percent is also more than 40m%.

Claims (9)

1. a weight, residual oil hydrocatalyst is characterized in that this catalyzer is the finish colloid that contains reactive metal molybdenum and/or tungsten, wherein MoS ₂, WS ₂Median size be lower than 500nm, the content of reactive metal is 1～20m%; Contain dispersion agent 0.1～10.0m% in the finish colloid, dispersion agent comprises one or more in tween, class of department, OP, Fatty Alcohol(C12-C14 and C12-C18) and the alicyclic organic tensio-active agent; Solvent in the finish colloid is 100 ℃～500 ℃ intermediates in the refinery.

2. according to the described hydrogenation catalyst of claim 1, it is characterized in that the content of said dispersion agent in catalyzer is 0.5～2.0m%.

3. according to the described hydrogenation catalyst of claim 1, it is characterized in that containing in the catalyzer stablizer, the content in catalyzer is 0.1～10.0m%.

4. according to the described hydrogenation catalyst of claim 3, it is characterized in that said stablizer comprises long chain alkane, naphthenic hydrocarbon, polycyclic aromatic hydrocarbons and derivative thereof and/or wax, its content is 0.5～2.0m%.

5. according to the described hydrogenation catalyst of claim 1, it is characterized in that said solvent is one or more among lubricating oil, machine oil, wax oil, gasoline, diesel oil, kerosene and/or the VGO.

6. the described hydrogenization catalyst preparation method of claim 1 is characterized in that: require MoS according to each components contents in the catalyzer ₂And/or WS ₂Powder mixes with solvent phase and places reaction vessel, and in mixture, add dispersion agent and stablizer, in the presence of hydrogen, stirred 2～8 hours in 60 ℃～100 ℃, and at 300 ℃～400 ℃, kept under the condition of pressure 5～15MPa 4～10 hours, and constantly stir, leave standstill and isolate throw out then at room temperature, promptly obtain the colloid finish of catalyzer; Wherein said MoS ₂And WS ₂Powder diameter is below 1 micron.

7. according to the described preparation method of claim 6, it is characterized in that said time of repose is 15～45 days.

8. the application of the described catalyzer of claim 1 in hydrocracking process of suspended bed is characterized in that catalyst levels counts 50～5000 μ g/g with metal; Operational condition is: pressure 2～20MPa, 300～470 ℃ of temperature, liquid hourly space velocity 0.2～2.Oh ^-1, hydrogen to oil volume ratio 200～1200.

9. according to the described application of claim 8, it is characterized in that catalyst levels counts 50～500 μ g/g with metal; Operational condition is: pressure 8～14MPa, 350～450 ℃ of temperature, liquid hourly space velocity 0.7～2.0h ^-1, hydrogen to oil volume ratio 500～1000.