CN1470327A - Metal nitride catalyst preparing method and catalyst - Google Patents

Metal nitride catalyst preparing method and catalyst Download PDF

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CN1470327A
CN1470327A CNA021256063A CN02125606A CN1470327A CN 1470327 A CN1470327 A CN 1470327A CN A021256063 A CNA021256063 A CN A021256063A CN 02125606 A CN02125606 A CN 02125606A CN 1470327 A CN1470327 A CN 1470327A
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catalyst
nitride
temperature
preparation
molecular sieve
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CN1230251C (en
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周志军
孙桂大
田晓飞
王萍
李翠清
李凤艳
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China Petroleum and Chemical Corp
China Petrochemical Corp
Beijing Institute of Petrochemical Technology
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Beijing Institute of Petrochemical Technology
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Abstract

The invention provides a kind of active metal nitride catalyst which is used to desulphurize, denitrogen and decrease olefin. The nitride can exist alone as compound or on the carrier material. The load quantity is 15-35%. The hole volume of the catalyst reach 0.29-0.63cm2/g, the rate surface area reach 165-232m2/g. the invention also discloses the manufacturing method, uses hydrogen and nitrogen as reducer, and uses method of procedure heat reducing.

Description

A kind of metal nitride catalyst agent preparation method and catalyst
Technical field
The preparation method who the present invention relates to a kind of nitride catalyst reaches with the prepared a kind of catalyst of this method, specifically a kind of nitride hydrodenitrogeneration, hydrodesulfurization and hydrogenation and olefin hydrocarbon removal catalyst.
Background technology
Hydrocarbons hydrogenation is refining to be technical process necessary in the petrochemical industry, its objective is organic sulfur compound and the organic nitrogen compound removed in the feedstock oil, to satisfy the high-quality requirement of oil product.Along with the sustainable growth of national economy, the oil product demand is increased year by year, crude oil heaviness, inferiorization trend are also serious day by day, cause oil product (gasoline, diesel oil, kerosene) harmful substance (SO in application process x, NO xDeng) discharge capacity significantly increase, particularly the urban air pollution problem that causes of motor-vehicle tail-gas is serious day by day, has caused the close attention and the great attention of government and environmental administration.Therefore, must carry out deep hydrofinishing,, improve the quality of oil product to remove impurity such as sulphur, nitrogen and aromatic hydrocarbons wherein to crude oil fractions.
For a long time, people have carried out deeply the desulfurization of fuel oil and denitrogenation hydrogenation catalyst for refining and method and extensive studies has proposed many desulfurization removing nitric Hydrobon Catalyst And Its Preparation Method and hydrogenation desulfurization and denitrogenation methods with high catalytic activity always.
At present, industrial hydrodesulfurization commonly used (HDS) hydrodenitrogeneration (HDN) catalyst is cobalt-molybdenum or nickel-molybdenum catalyst, sometimes also add some auxiliary agents,, can't satisfy the requirement of oil product deep desulfuration, denitrogenation though these catalyst have certain desulfurization removing nitric activity as phosphorus and so on.
Chinese patent CN1067654C discloses a kind of double elements bigger serface transition metal nitride, this metal nitride is to be mixed by the nitrate that contains transition metal or sulfate solution and Cr, Mo or W acid or Cr, Mo or W acid aqueous ammonium, make support type or non-loading type double elements slaine or composite oxides by coprecipitation or infusion process, again with double elements slaine or the logical NH of composite oxides 3Carry out temperature programming, react under final nitriding temperature 600-750 ℃ and make.This method NH 3Be nitridizing agent, and NH 3In nitridation process, be easy to take place hydrothermal sintering, make the specific surface of catalyst be restricted, and can not obtain the catalyst of Large ratio surface.And this method for the requirement of equipment performance also than higher, simultaneously poor stability, be not easy to operation.In addition, also can cause pollution to a certain degree, be unfavorable for environmental protection.
Summary of the invention
One of purpose of the present invention is, a kind of preparation method of metal nitride catalyst agent is provided.Another object of the present invention is to, a kind of metal nitride catalyst agent that has than bigger serface is provided.
The invention provides a kind of metal nitride catalyst agent, catalyst is an active component with the nitride of group vib and/or group VIII metal, and loads on the carrier material, and the pore volume of catalyst is 0.29-0.63cm 3/ g, specific area is 165-232m 2/ g, discloseder nitride catalyst has great advantage.
Wherein the load capacity of nitride is 15%-35% by weight.
Described nitride is tungsten nitride or nickel oxide tungsten preferably.
Described carrier material can be any porous mass with suitable specific area.Comprise:
Metal oxide, as: γ-Al 2O 3, TiO 2, TiO 2-Al 2O 3Deng; Natural clay, as: bentonite, kaolin etc.; Molecular sieve, as: phosphate aluminium molecular sieve, ZSM5 type molecular sieve, MCM molecular sieve etc.
Wherein best carrier is: γ-Al 2O 3, TiO 2, TiO 2-Al 2O 3Or phosphate aluminium molecular sieve.
Simultaneously, the present invention also provides a kind of preparation method of metal nitride catalyst agent, adopts group vib and/or group VIII metallic compound temperature-programmed reduction method to prepare catalyst of the present invention, and used reducing agent is hydrogen and nitrogen in the temperature programming process.
Concrete preparation process is:
1, preparation catalyst precarsor: with group vib and/or the dissolving of group VIII slaine, drying was also calcined 4 hours under 673K-823K at least, preferably 4-10 hour, made composite oxides;
2, above-mentioned composite oxides are carried out temperature programmed reduction, preparation nitride: in the presence of hydrogen and nitrogen, be warming up to 823K～923K, and under this temperature, reduced at least 2 hours, preferably 2-4 hour, and at room temperature, passivation is at least 8 hours in the inert gas atmosphere, preferably 8-15 hour, obtain catalyst of the present invention.
Said group vib and/or group VIII slaine in the above-mentioned steps 1 better are tungstates or nickel salt, preferably ammonium metatungstate, ammonium tungstate, nickel nitrate or nickelous carbonate.Also the reactive metal aqueous solution can be impregnated on the carrier material dry again in the step 1 after the dissolving.
Described carrier material can be any porous carrier materials with suitable specific area, comprising: metal oxide, as: γ-Al 2O 3, TiO 2Deng; Natural clay, as: bentonite, kaolin etc.; Molecular sieve, as: ZSM5 type molecular sieve, phosphate aluminium molecular sieve, MCM series molecular sieve etc.
Wherein best carrier is: γ-Al 2O 3, TiO 2, TiO 2-Al 2O 3Or phosphate aluminium molecular sieve.
Said 823K～the 923K that is warming up in the step 2 can adopt linear mode to heat up or temperature-gradient method.Linear mode heats up and is the heating rate intensification with 0.5-3K/min; The heating mode of segmentation rises to 523K～723K for first heating rate with 3-4K, and the heating rate with 0.5-1K is warming up to 823K～923K again.
Said inert gas is preferably nitrogen or helium in the step 2, preferably contains the nitrogen of oxygen 0.5-1%.
It is nitridizing agent that the present invention adopts nitrogen and hydrogen, has synthesized tungsten nitride and nickel oxide tungsten Hydrobon catalyst.Compare with sulfide catalyst in the past, this type of catalyst has higher specific area and higher hydrodesulfurization and hydrodenitrogeneration catalytic activity, can remove the big molecule sulfur-containing compound of condensed-nuclei aromatics.Because nitride catalyst does not need the pre-vulcanization process of tradition sulfuration catalyst series before carrying out hydrodesulfurization, denitrification reaction, belong to process for cleanly preparing; And nitridizing agent adopts hydrogen and nitrogen in the preparation process, and than being that nitridizing agent more meets environmental protection requirement with ammonia, and to the requirement reduction of equipment, stable production process is better.
The specific embodiment
Embodiment 1 preparation non-loading type tungsten nitride (W 2N) preparation method of catalyst 11. catalyst precarsors:
Getting the 13.04g ammonium metatungstate is dissolved in the 200ml distilled water; Water bath method; The material that obtains is dry 10h under 393K (120 ℃) temperature; At 773K (500 ℃) temperature lower calcination 6h.2. the temperature programmed reduction tungsten oxide prepares tungsten nitride (W 2N)
Hydrogen stream (99.999%, 90ml/min) and nitrogen stream (99.999%, the 18ml/min) tungsten oxide precursor of the above-mentioned preparation of reduction down, temperature is elevated to 923K (650 ℃) with linear mode, programming rate 1K/min; After the reduction, the sample of black is at room temperature at 1%O 2/ N 2Passivation 10h (before being exposed to air) in the gas (30ml/min).N 2Available He replaces.
Embodiment 2 preparation non-loading type tungsten nitride (W 2N) preparation method of catalyst 21. catalyst precarsors:
Claim the 13.04g ammonium metatungstate to be dissolved in the 200ml distilled water; Water bath method; The material that obtains is dry 10h under 393K (120 ℃) temperature; Prepare tungsten nitride (W at 773K (500 ℃) temperature lower calcination 6h.2. temperature programmed reduction tungsten oxide 2N)
Hydrogen stream (99.999%, 90ml/min) and nitrogen stream (99.999%, the 18ml/min) tungsten oxide precursor of the above-mentioned preparation of reduction down, programming rate is raised to 623K (350 ℃) with 3K/min earlier and is raised to 923K (650 ℃) with 1K/min again; After reduction, the sample of black is at room temperature at 1%O 2/ N 2Passivation 10h (before being exposed to air) in the gas (30ml/min).N 2Available He replaces.
Embodiment 3 support type nitrogenize tungsten (W 2N/ γ-Al 2O 3) preparation method of Preparation of catalysts 11. catalyst precarsors:
Taking by weighing the 2.165g ammonium metatungstate is dissolved in the 100ml distilled water; Claim 3.46 gram γ-Al 2O 3, be immersed in the above-mentioned solution and spend the night; Water bath method; The material that obtains is dry 10h under 393K (120 ℃) temperature; At 773K (500 ℃) temperature lower calcination 6h; 2. the temperature programmed reduction tungsten oxide prepares tungsten nitride (W 2N)
Hydrogen stream (99.999%, 90ml/min) and nitrogen stream (99.999%, the 18ml/min) material after the above-mentioned calcining of reduction down, temperature is elevated to 923K (650 ℃) with linear mode, programming rate 1K/min; After the reduction, the sample of black is at room temperature at 1%O 2/ N 2Passivation 10h (before being exposed to air) in the gas (30ml/min), N 2Available He replaces;
The load capacity of tungsten nitride is about 24% (weight meter);
The specific surface of catalyst sample is 197m 2/ g, pore volume 0.53cm 3/ g.
4 years type tungsten nitrides of embodiment (W 2N/ γ-Al 2O 3) preparation method of Preparation of catalysts 21. catalyst precarsors:
Taking by weighing the 2.165g ammonium metatungstate is dissolved in the 100ml distilled water; Claim 3.46 gram γ-Al 2O 3, be immersed in the above-mentioned solution and spend the night; Water bath method; The material that obtains is dry 10h under 393K (120 ℃) temperature; At 773K (500 ℃) temperature lower calcination 6h; 2. the temperature programmed reduction tungsten oxide prepares tungsten nitride (W 2N)
Hydrogen stream (99.999%, 90ml/min) and nitrogen stream (99.999%, the 18ml/min) material after the above-mentioned calcining of reduction down, programming rate is raised to 623K (350 ℃) with 3K/min earlier and is raised to 923K (650 ℃) with 1K/min again; After reduction, the sample of black is at room temperature at 1%O 2/ N 2Passivation 10h (before being exposed to air) in the gas (30ml/min).N 2Available He replaces;
The load capacity of tungsten nitride is about 24% (weight meter);
The specific surface of catalyst sample is 216m 2/ g, pore volume 0.58cm 3/ g.
Embodiment 5 non-loading type tungsten nitride (W 2N) mensuration of catalyst HDS activity
Stagnation pressure 3.0MPa is carried out in model compound thiophene hydrodesulfurization catalysis experiment on the continuous micro-reactor of high pressure.1) gets 1mlW 2The N catalyst; 2) catalyst will activate before using, at 673K and 0.1MPa H 2/ N 2Or H 2Activation 4h is with the W from passivation 2The N catalyst surface is removed O 23) liquid reactants is thiophene content 5% cyclohexane solution, squeezes in the reactor by high-pressure pump; 4) product stream is used the chromatogram that has fid detector by on-line analysis; 5) desulfurization degree is up to 93%.
Embodiment 6 non-loading type tungsten nitride (W 2N) mensuration of catalyst HDN activity
The hydrodenitrogeneration catalysis experiment of model compound pyridine is being carried out stagnation pressure 3.0MPa on the micro-reactor continuously.1) measures 1ml W 2The N catalyst; 2) catalyst will activate before using, at 673K and 0.1MPa H 2/ N 2Or H 2Activation 4h is with the W from passivation 2The N catalyst surface is removed O 23) liquid reactants is thiophene content 5% cyclohexane solution, squeezes in the reactor by high-pressure pump; 4) product stream is used the chromatogram that has fid detector by on-line analysis; 5) denitrification percent is up to 87%.
Embodiment 7 support type nitrogenize tungsten (W 2N/ γ-Al 2O 3) mensuration of catalyst HDS activity
The model compound thiophene gets hydrodesulfurization catalysis experiment and is carrying out stagnation pressure 3.0MPa on the micro-reactor continuously.1) measures 1ml W 2N/ γ-Al 2O 3Catalyst; 2) catalyst will activate before using, at 673K and 0.1MPa H 2/ N 2Or H 2Activation 4h is with the W from passivation 2The N catalyst surface is removed O 23) liquid reactants is thiophene content 5% cyclohexane solution, squeezes in the reactor by high-pressure pump; 4) product stream is used the chromatogram that has fid detector by on-line analysis; 5) desulfurization degree is up to 96%.The preparation method of preparation 1. catalyst precarsors of embodiment 8 non-loading type nickel oxide tungsten catalysts
Taking by weighing 0.5449g nickel nitrate and 1.968g ammonium metatungstate is dissolved in the 200ml distilled water; Water bath method; The material that obtains is dry 10h under 393K (120 ℃) temperature; At 773K (500 ℃) temperature lower calcination 6h.2. temperature programmed reduction prepares catalyst
Hydrogen stream (99.999%, 90ml/min) and nitrogen stream (99.999%, the 18ml/min) catalyst precarsor of the above-mentioned preparation of reduction down, temperature is elevated to 923K (650 ℃) with linear mode, programming rate 1K/min.After reduction, the sample of black is at room temperature at 1%O 2/ N 2Passivation 10h (before being exposed to air) in the gas (30ml/min).N 2Available He replaces.
The preparation method of preparation 1. catalyst precarsors of embodiment 9 support type nitrogenize nickel tungsten catalysts
Taking by weighing 0.5449g nickel nitrate and 1.968g ammonium metatungstate is dissolved in the 200ml distilled water; Claim 3.46 gram γ-Al 2O 3, be immersed in the above-mentioned solution and spend the night; Water bath method; The material that obtains is dry 10h under 393K (120 ℃) temperature; At 773K (500 ℃) temperature lower calcination 6h; 2. temperature programmed reduction prepares catalyst
Hydrogen stream (99.999%, 90ml/min) and nitrogen stream (99.999%, the 18ml/min) material after the above-mentioned calcining of reduction down, temperature is elevated to 923K (650 ℃) with linear mode, programming rate 1K/min; After reduction, the sample of black is at room temperature at 1%O 2/ N 2Passivation 10h (before being exposed to air) in the gas (30ml/min).N 2Available He replaces; The load capacity of nickel oxide tungsten is about 24% (weight meter);
The specific surface of catalyst sample is 227m 2/ g, pore volume 0.63cm 3/ g.
The mensuration of embodiment 10 non-loading type nickel oxide tungsten catalyst HDS activity
The model compound thiophene gets hydrodesulfurization catalysis experiment and is carrying out stagnation pressure 3.0MPa on the micro-reactor continuously.
1) measures 1ml non-loading type nickel oxide tungsten catalyst;
2) catalyst will activate before using, at 673K and 0.1MPa H 2/ N 2Or H 2Activation 4h, with
Remove O from the passivated catalyst surface 2
3) liquid reactants is thiophene content 5% cyclohexane solution, squeezes in the reactor by high-pressure pump;
4) product stream is used the chromatogram that has fid detector by on-line analysis;
5) desulfurization degree is up to 95%.
The mensuration of embodiment 11 non-loading type nickel oxide tungsten catalyst HDN activity
The hydrodenitrogeneration catalysis experiment of model compound pyridine is being carried out stagnation pressure 3.0MPa on the micro-reactor continuously.
1) gets 1ml non-loading type nickel oxide tungsten catalyst;
2) catalyst will activate before using, at 673K and 0.1MPa H 2/ N 2Or H 2Activation 4h,
To remove O from the passivated catalyst surface 2
3) liquid reactants is thiophene content 5% cyclohexane solution, squeezes in the reactor by high-pressure pump;
4) product stream is used the chromatogram that has fid detector by on-line analysis;
5) denitrification percent is up to 90%.The mensuration (embodiment 12) of 12 support type nitrogenize nickel tungsten catalyst HDS activity
The hydrodesulfurization catalysis experiment of model compound thiophene is being carried out stagnation pressure 3.0MPa on the micro-reactor continuously.
1) measures 1ml support type nitrogenize nickel tungsten catalyst;
2) catalyst will activate before using, at 673K and 0.1MPa H 2/ N 2Or H 2Activation 4h,
To remove O from the passivated catalyst surface 2
3) liquid reactants is thiophene content 5% cyclohexane solution, squeezes in the reactor by high-pressure pump;
4) product stream is used the chromatogram that has fid detector by on-line analysis;
5) desulfurization degree is up to 97%.
The mensuration of embodiment 13 support type nitrogenize nickel tungsten catalyst HDN activity
The hydrodenitrogeneration catalysis experiment of model compound pyridine is being carried out stagnation pressure 3.0MPa on the micro-reactor continuously.
1) 1ml support type nitrogenize nickel tungsten catalyst;
2) catalyst will activate before using, at 673K and 0.1MPa H 2/ N 2Or H 2The activation 4h, with from
O is removed on the passivated catalyst surface 2
3) liquid reactants is thiophene content 5% cyclohexane solution, squeezes in the reactor by high-pressure pump;
4) product stream is used the chromatogram that has fid detector by on-line analysis;
5) denitrification percent is up to 98%.
By above experimental data as seen, nitride catalyst can be prepared, and the load type nitrogen compound catalyst of Large ratio surface can be prepared with higher desulfurization, denitrification activity with method of the present invention.

Claims (10)

1. a metal nitride catalyst agent is characterized in that, is active component with the nitride of group vib and/or group VIII metal, and loads on the carrier material that the pore volume of catalyst is 0.29-0.63cm 3/ g, specific area is 165-232m 2/ g.
2. according to the described catalyst of claim 1, it is characterized in that the load capacity of nitride is 15%-35% by weight.
3. according to the described catalyst of claim 1, it is characterized in that nitride wherein is tungsten nitride or nickel oxide tungsten.
4. according to claim 1,2 or 3 described catalyst, it is characterized in that carrier material wherein is one or more in metal oxide, molecular sieve, silica gel, diatomite, the natural clay.
5. according to the described catalyst of claim 4, it is characterized in that metal oxide wherein is γ-Al 2O 3, TiO 2TiO 2-Al 2O 3Natural clay is bentonite, kaolin; Molecular sieve is phosphate aluminium molecular sieve, ZSM5 type molecular sieve, MCM molecular sieve.
6. the preparation method of a metal nitride catalyst agent adopts group vib and/or group VIII metallic compound temperature-programmed reduction method to prepare catalyst, it is characterized in that used reducing agent is hydrogen and nitrogen in the temperature programming process.
7. according to the described preparation method of claim 6, it is characterized in that concrete preparation process is:
(1), preparation catalyst precarsor:, make composite oxides with the dissolving of group vib and/or group VIII slaine, dry and calcining at least 4 hours under 673K-823K;
(2), above-mentioned composite oxides are carried out temperature programmed reduction, preparation nitride: in the presence of hydrogen and nitrogen, be warming up to 823K～923K, and under this temperature, reduced at least 2 hours, and at room temperature, passivation is at least 8 hours in the inert gas atmosphere, obtains catalyst of the present invention.
8. according to the described preparation method of claim 7, it is characterized in that wherein the said 823K～923K that is warming up in the step (2) adopts linear mode to heat up or temperature-gradient method.
9. according to the described preparation method of claim 8, it is characterized in that said linear temperature increase is the heating rate intensification with 0.5-3K/min.
10. according to the described preparation method of claim 9, it is characterized in that said temperature-gradient method rises to 523K～723K for first heating rate with 3-4K, the heating rate with 0.5-1K is warming up to 823K～923K again.
CN 02125606 2002-07-24 2002-07-24 Metal nitride catalyst preparing method and catalyst Expired - Fee Related CN1230251C (en)

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CN106147859A (en) * 2016-08-18 2016-11-23 锡山区绿春塑料制品厂 A kind of residuum hydrodesulfurization RFCC group technology of sour crude
CN106167719A (en) * 2016-08-18 2016-11-30 锡山区绿春塑料制品厂 A kind of hydrorefining basic oil lubricating oil technique
CN106167716A (en) * 2016-08-18 2016-11-30 锡山区绿春塑料制品厂 A kind of coker gas oil hydrofining technology
CN106190243A (en) * 2016-08-12 2016-12-07 锡山区绿春塑料制品厂 A kind of FCC gasoline hydrodesulfurization
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CN106190302A (en) * 2016-08-19 2016-12-07 锡山区绿春塑料制品厂 A kind of catalytic cracking combined technique of delayed coking hydrofinishing
CN106190262A (en) * 2016-08-18 2016-12-07 锡山区绿春塑料制品厂 A kind of straight-run naphtha hydrofining technology
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CN106190255A (en) * 2016-08-17 2016-12-07 锡山区绿春塑料制品厂 A kind of straight-run naphtha hydrofining technology
CN106190234A (en) * 2016-08-10 2016-12-07 锡山区绿春塑料制品厂 A kind of coker gas oil hydrofining technology
CN106190296A (en) * 2016-08-17 2016-12-07 锡山区绿春塑料制品厂 A kind of residuum hydrodesulfurization RFCC group technology of sour crude
CN106190246A (en) * 2016-08-12 2016-12-07 锡山区绿春塑料制品厂 A kind of coking gasoline hydrogenation refining technique
CN106190247A (en) * 2016-08-12 2016-12-07 锡山区绿春塑料制品厂 A kind of aerial kerosene hydrofining technology
CN106190233A (en) * 2016-08-10 2016-12-07 锡山区绿春塑料制品厂 A kind of FCC gasoline hydrodesulfurization
CN106190294A (en) * 2016-08-11 2016-12-07 锡山区绿春塑料制品厂 A kind of residuum hydrodesulfurization RFCC group technology of sour crude
CN106190257A (en) * 2016-08-16 2016-12-07 锡山区绿春塑料制品厂 A kind of straight-run naphtha hydrofining technology
CN106190309A (en) * 2016-08-16 2016-12-07 锡山区绿春塑料制品厂 A kind of hydrorefining paraffin wax technique
CN106190241A (en) * 2016-08-12 2016-12-07 锡山区绿春塑料制品厂 A kind of waste lubricant oil by hydrogenation regeneration technology
CN106190298A (en) * 2016-08-19 2016-12-07 锡山区绿春塑料制品厂 A kind of residuum hydrodesulfurization RFCC group technology of sour crude
CN106190299A (en) * 2016-08-23 2016-12-07 锡山区绿春塑料制品厂 A kind of residuum hydrodesulfurization RFCC group technology of sour crude
CN106190249A (en) * 2016-08-12 2016-12-07 锡山区绿春塑料制品厂 A kind of waste lubricant oil by hydrogenation regeneration technology
CN106190251A (en) * 2016-08-16 2016-12-07 锡山区绿春塑料制品厂 A kind of coking gasoline hydrogenation refining technique
CN106190265A (en) * 2016-08-19 2016-12-07 锡山区绿春塑料制品厂 A kind of FCC gasoline hydrodesulfurization
CN106190268A (en) * 2016-08-19 2016-12-07 锡山区绿春塑料制品厂 Coalite tar hydrofining technology in one
CN106190301A (en) * 2016-08-19 2016-12-07 锡山区绿春塑料制品厂 A kind of catalytic cracking combined technique of delayed coking hydrofinishing
CN106190240A (en) * 2016-08-11 2016-12-07 锡山区绿春塑料制品厂 A kind of coker gas oil hydrofining technology
CN106190295A (en) * 2016-08-12 2016-12-07 锡山区绿春塑料制品厂 A kind of residuum hydrodesulfurization RFCC group technology of sour crude
CN106190237A (en) * 2016-08-11 2016-12-07 锡山区绿春塑料制品厂 A kind of FCC gasoline hydrodesulfurization
CN106190238A (en) * 2016-08-11 2016-12-07 锡山区绿春塑料制品厂 A kind of waste lubricant oil by hydrogenation regeneration technology
CN106190264A (en) * 2016-08-19 2016-12-07 锡山区绿春塑料制品厂 A kind of coker gas oil hydrofining technology
CN106190252A (en) * 2016-08-16 2016-12-07 锡山区绿春塑料制品厂 A kind of straight-run naphtha hydrofining technology
CN106190248A (en) * 2016-08-12 2016-12-07 锡山区绿春塑料制品厂 A kind of FCC gasoline hydrodesulfurization
CN106190260A (en) * 2016-08-19 2016-12-07 锡山区绿春塑料制品厂 A kind of straight-run naphtha hydrofining technology
CN106190263A (en) * 2016-08-19 2016-12-07 锡山区绿春塑料制品厂 A kind of hydrorefining paraffin wax technique
CN106190291A (en) * 2016-08-17 2016-12-07 锡山区绿春塑料制品厂 A kind of hydrorefining basic oil lubricating oil technique
CN106190281A (en) * 2016-08-16 2016-12-07 锡山区绿春塑料制品厂 A kind of hydrorefining basic oil lubricating oil technique
CN106190250A (en) * 2016-08-16 2016-12-07 锡山区绿春塑料制品厂 A kind of FCC gasoline hydrodesulfurization
CN106190236A (en) * 2016-08-11 2016-12-07 锡山区绿春塑料制品厂 A kind of straight-run naphtha hydrofining technology
CN106190261A (en) * 2016-08-19 2016-12-07 锡山区绿春塑料制品厂 A kind of FCC gasoline hydrodesulfurization
CN106190297A (en) * 2016-08-19 2016-12-07 锡山区绿春塑料制品厂 A kind of residuum hydrodesulfurization RFCC group technology of sour crude
CN106190222A (en) * 2016-08-12 2016-12-07 锡山区绿春塑料制品厂 A kind of biodiesel hydrogenation deoxidation technique
CN106190239A (en) * 2016-08-11 2016-12-07 锡山区绿春塑料制品厂 A kind of aerial kerosene hydrofining technology
CN106190310A (en) * 2016-08-17 2016-12-07 锡山区绿春塑料制品厂 A kind of hydrorefining paraffin wax technique
CN106190308A (en) * 2016-08-12 2016-12-07 锡山区绿春塑料制品厂 A kind of hydrorefining paraffin wax technique
CN106190254A (en) * 2016-08-17 2016-12-07 锡山区绿春塑料制品厂 A kind of coker gas oil hydrofining technology
CN106190270A (en) * 2016-08-23 2016-12-07 锡山区绿春塑料制品厂 A kind of coker gas oil hydrofining technology
CN106190253A (en) * 2016-08-17 2016-12-07 锡山区绿春塑料制品厂 A kind of biodiesel hydrogenation deoxidation technique
CN106190267A (en) * 2016-08-18 2016-12-07 锡山区绿春塑料制品厂 A kind of biodiesel hydrogenation deoxidation technique
CN106190293A (en) * 2016-08-17 2016-12-07 锡山区绿春塑料制品厂 A kind of waste lubricant oil by hydrogenation regeneration technology
CN106190266A (en) * 2016-08-18 2016-12-07 锡山区绿春塑料制品厂 A kind of FCC gasoline hydrodesulfurization
CN106190235A (en) * 2016-08-10 2016-12-07 锡山区绿春塑料制品厂 A kind of biodiesel hydrogenation deoxidation technique
CN106190242A (en) * 2016-08-11 2016-12-07 锡山区绿春塑料制品厂 A kind of coking gasoline hydrogenation refining technique
CN106190244A (en) * 2016-08-12 2016-12-07 锡山区绿春塑料制品厂 A kind of waste lubricant oil by hydrogenation regeneration technology
CN106190307A (en) * 2016-08-11 2016-12-07 锡山区绿春塑料制品厂 A kind of hydrorefining paraffin wax technique
CN106190245A (en) * 2016-08-12 2016-12-07 锡山区绿春塑料制品厂 A kind of hydrorefining basic oil lubricating oil technique
CN106190284A (en) * 2016-08-12 2016-12-07 锡山区绿春塑料制品厂 A kind of residuum hydrodesulfurization RFCC group technology of sour crude
CN106190258A (en) * 2016-08-17 2016-12-07 锡山区绿春塑料制品厂 A kind of coking gasoline hydrogenation refining technique
CN106190259A (en) * 2016-08-19 2016-12-07 锡山区绿春塑料制品厂 Coalite tar hydrofining technology in one
CN106190300A (en) * 2016-08-12 2016-12-07 锡山区绿春塑料制品厂 A kind of catalytic cracking combined technique of delayed coking hydrofinishing
CN106221798A (en) * 2016-08-11 2016-12-14 锡山区绿春塑料制品厂 A kind of residuum hydrodesulfurization RFCC group technology of sour crude
CN106221777A (en) * 2016-08-19 2016-12-14 锡山区绿春塑料制品厂 A kind of biodiesel hydrogenation deoxidation technique
CN106221750A (en) * 2016-08-19 2016-12-14 锡山区绿春塑料制品厂 A kind of hydrorefining basic oil lubricating oil technique
CN106221769A (en) * 2016-08-19 2016-12-14 锡山区绿春塑料制品厂 A kind of coker gas oil hydrofining technology
CN106221793A (en) * 2016-08-19 2016-12-14 锡山区绿春塑料制品厂 A kind of waste lubricant oil by hydrogenation regeneration technology
CN106221754A (en) * 2016-08-19 2016-12-14 锡山区绿春塑料制品厂 A kind of FCC gasoline hydrodesulfurization
CN106221737A (en) * 2016-08-12 2016-12-14 锡山区绿春塑料制品厂 A kind of FCC gasoline hydrodesulfurization
CN106221803A (en) * 2016-08-23 2016-12-14 锡山区绿春塑料制品厂 A kind of catalytic cracking combined technique of delayed coking hydrofinishing
CN106221738A (en) * 2016-08-12 2016-12-14 锡山区绿春塑料制品厂 A kind of diesel hydrogenation for removal sulphur denitrification process
CN106221724A (en) * 2016-08-23 2016-12-14 锡山区绿春塑料制品厂 A kind of biodiesel hydrogenation deoxidation technique
CN106221778A (en) * 2016-08-19 2016-12-14 锡山区绿春塑料制品厂 A kind of aerial kerosene hydrofining technology
CN106221801A (en) * 2016-08-19 2016-12-14 锡山区绿春塑料制品厂 A kind of residuum hydrodesulfurization RFCC group technology of sour crude
CN106221762A (en) * 2016-08-12 2016-12-14 锡山区绿春塑料制品厂 A kind of coking crude benzene hydrodesulfurization
CN106221759A (en) * 2016-08-11 2016-12-14 锡山区绿春塑料制品厂 A kind of aerial kerosene hydrofining technology
CN106221734A (en) * 2016-08-11 2016-12-14 锡山区绿春塑料制品厂 A kind of straight-run naphtha hydrofining technology
CN106221795A (en) * 2016-08-19 2016-12-14 锡山区绿春塑料制品厂 A kind of hydrorefining basic oil lubricating oil technique
CN106221780A (en) * 2016-08-19 2016-12-14 锡山区绿春塑料制品厂 A kind of hydrorefining basic oil lubricating oil technique
CN106221772A (en) * 2016-08-19 2016-12-14 锡山区绿春塑料制品厂 A kind of FCC gasoline hydrodesulfurization
CN106221743A (en) * 2016-08-17 2016-12-14 锡山区绿春塑料制品厂 A kind of straight-run naphtha hydrofining technology
CN106221771A (en) * 2016-08-19 2016-12-14 锡山区绿春塑料制品厂 A kind of coking crude benzene hydrodesulfurization
CN106221749A (en) * 2016-08-16 2016-12-14 锡山区绿春塑料制品厂 A kind of waste lubricant oil by hydrogenation regeneration technology
CN106221747A (en) * 2016-08-17 2016-12-14 锡山区绿春塑料制品厂 A kind of coking gasoline hydrogenation refining technique
CN106221799A (en) * 2016-08-16 2016-12-14 锡山区绿春塑料制品厂 A kind of residuum hydrodesulfurization RFCC group technology of sour crude
CN106221723A (en) * 2016-08-19 2016-12-14 锡山区绿春塑料制品厂 A kind of biodiesel hydrogenation deoxidation technique
CN106221757A (en) * 2016-08-23 2016-12-14 锡山区绿春塑料制品厂 A kind of coker gas oil hydrofining technology
CN106221760A (en) * 2016-08-11 2016-12-14 锡山区绿春塑料制品厂 A kind of FCC gasoline hydrodesulfurization
CN106221756A (en) * 2016-08-23 2016-12-14 锡山区绿春塑料制品厂 A kind of straight-run naphtha hydrofining technology
CN106221770A (en) * 2016-08-19 2016-12-14 锡山区绿春塑料制品厂 A kind of waste lubricant oil by hydrogenation regeneration technology
CN106221776A (en) * 2016-08-19 2016-12-14 锡山区绿春塑料制品厂 A kind of waste lubricant oil by hydrogenation regeneration technology
CN106221733A (en) * 2016-08-11 2016-12-14 锡山区绿春塑料制品厂 A kind of straight-run naphtha hydrofining technology
CN106221781A (en) * 2016-08-19 2016-12-14 锡山区绿春塑料制品厂 A kind of hydrorefining paraffin wax technique
CN106221782A (en) * 2016-08-19 2016-12-14 锡山区绿春塑料制品厂 A kind of coking gasoline hydrogenation refining technique
CN106221783A (en) * 2016-08-23 2016-12-14 锡山区绿春塑料制品厂 A kind of waste lubricant oil by hydrogenation regeneration technology
CN106221768A (en) * 2016-08-19 2016-12-14 锡山区绿春塑料制品厂 A kind of straight-run naphtha hydrofining technology
CN106221744A (en) * 2016-08-18 2016-12-14 锡山区绿春塑料制品厂 A kind of biodiesel hydrogenation deoxidation technique
CN106221802A (en) * 2016-08-12 2016-12-14 锡山区绿春塑料制品厂 A kind of catalytic cracking combined technique of delayed coking hydrofinishing
CN106221746A (en) * 2016-08-17 2016-12-14 锡山区绿春塑料制品厂 A kind of straight-run naphtha hydrofining technology
CN106221751A (en) * 2016-08-19 2016-12-14 锡山区绿春塑料制品厂 A kind of hydrorefining basic oil lubricating oil technique
CN106221736A (en) * 2016-08-12 2016-12-14 锡山区绿春塑料制品厂 A kind of aerial kerosene hydrofining technology
CN106221765A (en) * 2016-08-16 2016-12-14 锡山区绿春塑料制品厂 A kind of coker gas oil hydrofining technology
CN106221753A (en) * 2016-08-19 2016-12-14 锡山区绿春塑料制品厂 A kind of aerial kerosene hydrofining technology
CN106221741A (en) * 2016-08-17 2016-12-14 锡山区绿春塑料制品厂 A kind of hydrorefining basic oil lubricating oil technique
CN106221722A (en) * 2016-08-19 2016-12-14 锡山区绿春塑料制品厂 A kind of biodiesel hydrogenation deoxidation technique
CN106221752A (en) * 2016-08-19 2016-12-14 锡山区绿春塑料制品厂 A kind of waste lubricant oil by hydrogenation regeneration technology
CN106221763A (en) * 2016-08-17 2016-12-14 锡山区绿春塑料制品厂 A kind of aerial kerosene hydrofining technology
CN106221740A (en) * 2016-08-12 2016-12-14 锡山区绿春塑料制品厂 A kind of coker gas oil hydrofining technology
CN106221766A (en) * 2016-08-17 2016-12-14 锡山区绿春塑料制品厂 A kind of coker gas oil hydrofining technology
CN106221755A (en) * 2016-08-23 2016-12-14 锡山区绿春塑料制品厂 A kind of FCC gasoline hydrodesulfurization
CN106221767A (en) * 2016-08-19 2016-12-14 锡山区绿春塑料制品厂 A kind of aerial kerosene hydrofining technology
CN106221784A (en) * 2016-08-23 2016-12-14 锡山区绿春塑料制品厂 A kind of coking gasoline hydrogenation refining technique
CN106221742A (en) * 2016-08-17 2016-12-14 锡山区绿春塑料制品厂 Coalite tar hydrofining technology in one
CN106221779A (en) * 2016-08-19 2016-12-14 锡山区绿春塑料制品厂 A kind of straight-run naphtha hydrofining technology
CN106221775A (en) * 2016-08-19 2016-12-14 锡山区绿春塑料制品厂 A kind of diesel hydrogenation for removal sulphur denitrification process
CN106221774A (en) * 2016-08-19 2016-12-14 锡山区绿春塑料制品厂 A kind of biodiesel hydrogenation deoxidation technique
CN106221745A (en) * 2016-08-18 2016-12-14 锡山区绿春塑料制品厂 A kind of aerial kerosene hydrofining technology
CN106221735A (en) * 2016-08-11 2016-12-14 锡山区绿春塑料制品厂 A kind of coking gasoline hydrogenation refining technique
CN106221739A (en) * 2016-08-12 2016-12-14 锡山区绿春塑料制品厂 A kind of biodiesel hydrogenation deoxidation technique
CN106221773A (en) * 2016-08-19 2016-12-14 锡山区绿春塑料制品厂 A kind of FCC gasoline hydrodesulfurization
CN106221721A (en) * 2016-08-11 2016-12-14 锡山区绿春塑料制品厂 A kind of biodiesel hydrogenation deoxidation technique
CN106221800A (en) * 2016-08-17 2016-12-14 锡山区绿春塑料制品厂 A kind of residuum hydrodesulfurization RFCC group technology of sour crude
CN106221761A (en) * 2016-08-12 2016-12-14 锡山区绿春塑料制品厂 A kind of aerial kerosene hydrofining technology
CN106221805A (en) * 2016-08-23 2016-12-14 锡山区绿春塑料制品厂 A kind of hydrorefining paraffin wax technique
CN106221764A (en) * 2016-08-17 2016-12-14 锡山区绿春塑料制品厂 A kind of FCC gasoline hydrodesulfurization
CN106221758A (en) * 2016-08-11 2016-12-14 锡山区绿春塑料制品厂 Coalite tar hydrofining technology in one
CN106221796A (en) * 2016-08-19 2016-12-14 锡山区绿春塑料制品厂 A kind of waste lubricant oil by hydrogenation regeneration technology
CN106221748A (en) * 2016-08-17 2016-12-14 锡山区绿春塑料制品厂 A kind of FCC gasoline hydrodesulfurization
CN106244206A (en) * 2016-08-17 2016-12-21 锡山区绿春塑料制品厂 A kind of hydrorefining paraffin wax technique
CN106244234A (en) * 2016-08-19 2016-12-21 锡山区绿春塑料制品厂 A kind of catalytic cracking combined technique of delayed coking hydrofinishing
CN106244212A (en) * 2016-08-16 2016-12-21 锡山区绿春塑料制品厂 A kind of FCC gasoline hydrodesulfurization
CN106244210A (en) * 2016-08-17 2016-12-21 锡山区绿春塑料制品厂 A kind of diesel hydrogenation for removal sulphur denitrification process
CN106244205A (en) * 2016-08-10 2016-12-21 锡山区绿春塑料制品厂 Coalite tar hydrofining technology in one
CN106244207A (en) * 2016-08-17 2016-12-21 锡山区绿春塑料制品厂 A kind of aerial kerosene hydrofining technology
CN106244211A (en) * 2016-08-16 2016-12-21 锡山区绿春塑料制品厂 A kind of FCC gasoline hydrodesulfurization
CN106244311A (en) * 2016-08-19 2016-12-21 锡山区绿春塑料制品厂 A kind of waste lubricant oil by hydrogenation regeneration technology
CN106244194A (en) * 2016-08-17 2016-12-21 锡山区绿春塑料制品厂 A kind of aerial kerosene hydrofining technology
CN106244197A (en) * 2016-08-19 2016-12-21 锡山区绿春塑料制品厂 A kind of hydrorefining paraffin wax technique
CN106244233A (en) * 2016-08-19 2016-12-21 锡山区绿春塑料制品厂 A kind of catalytic cracking combined technique of delayed coking hydrofinishing
CN106244218A (en) * 2016-08-19 2016-12-21 锡山区绿春塑料制品厂 A kind of coking gasoline hydrogenation refining technique
CN106244208A (en) * 2016-08-17 2016-12-21 锡山区绿春塑料制品厂 Coalite tar hydrofining technology in one
CN106244209A (en) * 2016-08-17 2016-12-21 锡山区绿春塑料制品厂 A kind of residuum hydrodesulfurization RFCC group technology of sour crude
CN106244220A (en) * 2016-08-19 2016-12-21 锡山区绿春塑料制品厂 A kind of hydrorefining paraffin wax technique
CN106244199A (en) * 2016-08-23 2016-12-21 锡山区绿春塑料制品厂 Coalite tar hydrofining technology in one
CN106244230A (en) * 2016-08-16 2016-12-21 锡山区绿春塑料制品厂 A kind of catalytic cracking combined technique of delayed coking hydrofinishing
CN106244200A (en) * 2016-08-11 2016-12-21 锡山区绿春塑料制品厂 A kind of aerial kerosene hydrofining technology
CN106244216A (en) * 2016-08-19 2016-12-21 锡山区绿春塑料制品厂 A kind of coker gas oil hydrofining technology
CN106244214A (en) * 2016-08-19 2016-12-21 锡山区绿春塑料制品厂 A kind of coker gas oil hydrofining technology
CN106244198A (en) * 2016-08-19 2016-12-21 锡山区绿春塑料制品厂 A kind of straight-run naphtha hydrofining technology
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CN109092347A (en) * 2017-06-21 2018-12-28 神华集团有限责任公司 Hydrogenation catalyst and its preparation method and application
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