CN1172692A - Catalyst maceration extract and its preparation method - Google Patents
Catalyst maceration extract and its preparation method Download PDFInfo
- Publication number
- CN1172692A CN1172692A CN 96109048 CN96109048A CN1172692A CN 1172692 A CN1172692 A CN 1172692A CN 96109048 CN96109048 CN 96109048 CN 96109048 A CN96109048 A CN 96109048A CN 1172692 A CN1172692 A CN 1172692A
- Authority
- CN
- China
- Prior art keywords
- solution
- catalyst
- preparation
- concentration
- moo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
An impregnating solution containing Mo, Ni (Co) and P for preparing catalyst has high metallic concentration and stability (more than 3 years) and contains such components as MoO3 (45-80 g/100 ml), NiO (8-20 g/100 ml) and CoO (0-15 g/100 ml). The weight ratio of P to MoO3 is 0.08-0.18. Its pH value is 0-3.8.
Description
The present invention relates to the compound method of the catalyst impregnating solution of a kind of high concentration, high stability, particularly a kind ofly be used to prepare Mo, the Ni (Co) of hydrocarbon hydrogenizing treamtent catalyst, the compound method of P solution.
Hydrotreating catalyst adopts immersion process for preparing usually.Promptly, flood certain carrier (as Al with the solution that contains required active component (as Mo, Ni, Co, P etc.)
2O
3, SiO
2-Al
2O
3Deng).In preparation high activity immersion-type hydrotreating catalyst process, ran into many difficulties, and these difficulties are almost all relevant with maceration extract.For example, especially the maceration extract of ultrahigh concentration is usually unstable or very unstable for high concentration.Mo-Ni (the Co)-P/Al that therefore, prepare the superelevation tenor
2O
3Hydrotreating catalyst is difficult to adopt " a step infusion process " once to finish.And adopt two step or multistep infusion process or other methods, not only make the preparation process complexity, and may bring harmful effect some physical and chemical performance (as mechanical strength) of catalyst.
United States Patent (USP) 4,392,985 disclose the preparation method of a kind of Mo, Co, P solution.The main points of this method are: at first under agitation with ammonium molybdate (NH
4)
6Mo
7O
244H
2O is partially soluble in the water.Not dissolving part adds H under slowly stirring
3PO
4(85%) dissolving adds cobalt nitrate Co (NO again
3)
26H
2O.The solution that adopts this invention to make, every 100ml can contain 33.6g MoO
3, 6.3g CoO and 8.6g P.The solution pH value is lower than 1.2.United States Patent (USP) 4,444,905 have introduced a kind of Mo, the Ni of higher molybdenum concentration, method of P solution of preparing.These method main points are: by a certain percentage with MoO
3, H
2O and H
3PO
4(75%) makes pulpous state.Add a certain amount of nickelous carbonate in during＞15 minutes, be warming up to 93 ℃ and heating 2 hours under this temperature.Make bright green solution.According to the prepared solution of this method, every 100ml can contain 12-34gMoO
3, 2.0-5.6gNiO, 2.3-6.4g P.This solution at room temperature can be stablized 6 months.Such solution concentration for the high tenor of preparation, high-activity hydrogenation catalyst, still can not be finished in a step.
The objective of the invention is: (1) preparation high stability, Mo, the Ni (Co) of high concentration, P solution; (2) simplify the Catalyst Production process, reduce cost; (3) improve catalyst activity and mechanical strength.
Mo of the present invention, Ni (Co), P solution, every 100ml solution contains 45-80g MoO
3, 8-20g NiO, 0-15g CoO, P/MoO
3Weight ratio is 0.08-0.18.
High concentrated solution compound method of the present invention is: by the solution concentration requirement required phosphoric acid is added in the entry, make phosphate aqueous solution.Above-mentioned phosphate aqueous solution is joined in the molybdenum oxide of aequum.This system under agitation is heated to little boiling, makes the whole or most of dissolvings of molybdenum oxide.System temperature is reduced to 60-70 ℃, adds the basic nickel carbonate of requirement, be warming up to once more little boil and add thermal agitation basic nickel carbonate is all dissolved.Last heating evaporation is removed redundant moisture and is made solution concentration, makes Mo, Ni, the P solution of high concentration, high stability.In addition, can also be as required, before the solution evaporation and concentration, add nickel nitrate and/or cobalt nitrate in above-mentioned solution, stirring and dissolving is with the pH value of regulator solution, and increase Ni content or introduce the Co component, evaporation and concentration makes Mo, Ni (Co), the P solution of high concentration, high stability again.
The preparation process of solution of the present invention is as follows:
(1). phosphate aqueous solution is added in the molybdenum oxide, stir, slowly heat temperature raising is to little boiling, and is heated to molybdenum oxide all or most of dissolving.
(2). after above-mentioned solution is cooled to 60-70 ℃, slowly add basic nickel carbonate, place and be warming up to little boiling again after 15 minutes, be heated to sediment and dissolve substantially.(this impurity is brought into by impure raw material to remove insoluble impurities in filtration after reducing to room temperature.If use pure raw material, can save filtration step).
(3). as required, can in above-mentioned filtrate, add nickel nitrate and/or cobalt nitrate, with Mo, Ni, P or Mo, Ni, Co, the P solution that makes required PH.
(4). above-mentioned solution heating is concentrated into needed concentration.Prepared Mo, Ni (Co), P solution according to the present invention have following character:
(1). every 100ml solution can contain MoO
345-80g, NiO 8-20g, CoO 0-15g, P/MoO
3Weight ratio is 0.08-0.18.
(2). can prepare the solution of different PH as required.Solution pH value excursion is 0-3.8.
(3). this solution at room temperature can be stablized more than 3 years.
Advantage of the present invention is:
(1) Mo of the present invention, Ni (Co), P solution, preparation process is simple, easily row.
(2) Mo of the present invention, Ni (Co), P solution, metal M o and Ni (Co) concentration can be very.The hydrotreating catalyst that just can prepare high tenor through the single-steeping process.
(3). Mo of the present invention, Ni (Co), P solution, even also very stable under very high metal concentration.At room temperature can stablize and not produce muddiness or precipitation more than 3 years.
(4). catalyst of the present invention, the catalyst that its hydrotreatment reactivity ratio makes with commonsense method wants high.
For further specifying the present invention, enumerate following examples and comparative example.(A) the preparation embodiment 1 of .Mo, Ni (Co), P solution
20ml phosphoric acid (85%) is dissolved in the 600ml water.Under agitation solution is joined in the 100g molybdenum oxide.Be warming up to and littlely boil and heat 3 hours to the most of dissolving of molybdenum oxide.Be cooled to 60-70 ℃.Under agitation slowly add basic nickel carbonate 35g, be warming up to again and littlely boil and heated 3 hours, dissolve substantially to sediment.Filter.Filtrate is concentrated into 250ml.Embodiment 2
17ml phosphoric acid (85%) is dissolved in the 600ml water.Under agitation solution is joined in the 100g molybdenum oxide.Be warming up to little boil and heat all dissolved to molybdenum oxide in 4 hours.Filter.In filtrate, add the 87g nickel nitrate.Be concentrated into 250ml after the dissolving.Embodiment 3
The 10g nickel nitrate is joined in embodiment 1 prepared solution.Dissolving.The solution heating is concentrated into 200ml.Embodiment 4
The 15g cobalt nitrate is joined in embodiment 1 prepared solution.Dissolving.The solution heating is concentrated into 200ml.Make Mo, Ni, Co, P solution.Embodiment 5
To be concentrated into 160ml by embodiment 3 prepared solution heating.Embodiment 6
To be concentrated into 130ml by embodiment 3 prepared solution heating.Embodiment 7
40ml phosphoric acid (85%) is dissolved in the 600ml water.Under agitation solution is joined in the 100g molybdenum oxide.Be warming up to and littlely boil and heat 3 hours to the most of dissolving of molybdenum oxide.Be cooled to 60-70 ℃, under agitation slowly add the 45g basic nickel carbonate.Be warming up to again and littlely boil and heated 3 hours, dissolve substantially to sediment.Filter.Filtrate is concentrated into 200ml.Comparative example 1
With 313ml water (21 ℃), 5.0ml phosphoric acid (75%) and 100g molybdenum oxide are made pulpous state.Slowly add 28.5g nickelous carbonate (adding more than 15 minutes).Mixture is heated to 93 ℃ then, stirs, and under this temperature, kept 2 hours.With the solution concentration that makes to 347ml.Comparative example 2
Comparative example 1 prepared solution heating is concentrated into 200ml.More than Mo, Ni, P and Mo, Ni, Co, the physico-chemical property of P solution of each routine gained list in the table 1.
The character of each routine solution of table 1
Solution concentration, g/l00ml
PH MoO
3NiO CoO P P/MoO
3Weight ratio stability * embodiment 1 3.0 40.0 8.0-3.6 are embodiment 2 0.1 40.0 8.9-3.0 embodiment 3 1.9 50.0 11.2-4.5 embodiment embodiment 5 1.6 62.5 14.0-5.6 embodiment 6 1.4 76.9 17.2-6.9 embodiment 7 1.3 50.0 12.9-9.0 0.05 0.5 years comparative example 2 2.1 39.5 8.3-2.1 of comparative example 1 3.0 22.8 4.8-1.2,0.05 concentration process more than 0.18 3 more than 0.09 3 more than 0.09 3 more than 4 1.8 50.0 10.0 1.9 4.5 0.09 3 years more than 0.09 3 more than 0.08 3 more than 0.09 3
Precipitation * occurring at room temperature places
As can be seen from Table 1, not only concentration is high but also extremely stable for the solution of embodiment 1-7.Solution in the comparative example, concentration have raising precipitation just to occur slightly, become unstable.
(B). verify beneficial effect embodiment 8 of the present invention by the preparation hydrotreating catalyst
Take by weighing 100g γ-Al
2O
3, add Mo, Ni, the P solution of 130ml according to (A) embodiment 3 preparations, at room temperature flood 4 hours after, leach redundant solution.Moist catalysis was dried 3 hours down at 105-115 ℃ after air drying spends the night.Dried sample is warming up to 190 ℃ with 3-5 ℃ of/minute speed, constant temperature 0.5 hour.Be warming up to 368 ℃ with 3-5 ℃ of/minute speed again, constant temperature 1 hour.Be warming up to 470 ℃ with 3-5 ℃ of/minute speed at last, constant temperature calcining 3 hours.Embodiment 9
Employing is a maceration extract according to the solution of (A) embodiment 5 preparations.Method for preparing catalyst and step are with embodiment 8.Comparative example 3
Employing is a maceration extract according to the solution of (A) comparative example 1 preparation.Method for preparing catalyst and step are with embodiment 8.Comparative example 4
The catalyst that comparative example 1 is made is used according to the solution impregnation of (A) comparative example 1 preparation the 2nd time.Dipping, drying, roasting condition are with embodiment 8.More than each routine prepared MoNiP/Al
2O
3Catalyst and used γ-Al
2O
3Physico-chemical property list in table 2 and the table 3 respectively.Raw materials used oil properties of evaluation of catalyst activity and reaction process condition see Table 4 and table 5.
Evaluate catalysts was vulcanized respectively under 260 ℃ and 370 ℃ 8 hours with the grand celebration aviation kerosine cut that contains carbon disulfide 1.5% (V).Sulfuration finishes, and swap-in feedstock oil is stablized after 8 hours and begun to test.When estimating each routine catalyst, by the conditioned reaction temperature, make total denitrification percent reach 95w%, promptly generating oily nitrogen content is 0.06w%.When catalyst than low reaction temperatures the time, just can reach this denitrification percent, show that this catalyst has higher activity.Vice versa.
Table 6 is listed each routine catalyst hydrogenation denitrification reaction activity rating result.
From table 3 and table 6 result as can be seen: the catalyst that adopts the present invention's preparation, hydrodenitrogenationactivity activity is much higher, compares reaction temperature with common single-steeping method and will hang down 13 ℃ (embodiment 8 compares with comparative example 3) or low 19 ℃ (embodiment 9 compares with comparative example 3).Compare with common secondary dipping process, although step is simple, reaction temperature still will be hanged down 7 ℃ (embodiment 9 compares with comparative example 3).In addition, hydrotreating catalyst of the present invention, aspect physico-chemical property, mechanical strength for example, aspects such as specific area and pore volume all are better than common secondary dipping process.
Used γ-the Al of table 2 each routine catalyst of preparation
2O
3Physico-chemical property
Specific area, M
2/ g 308
Pore volume, ml/g 0.607
Average pore diameter, nm 7.76
Mechanical strength, N/mm
*17.3* Ф 1.0mm strip
The physico-chemical property of each routine catalyst of table 3
Embodiment 8 embodiment 9 comparative examples 3 comparative examples 4 specific surfaces, m
2/ g 162 138 195 127 pore volumes, ml/g 0.320 0.300 0.380 0.290 average pore diameter, nm 8.16 8.23 7.93 8.19 chemical compositions, w%MoO
324.1 29.6 16.8 28.9NiO, 4.31 5.60 3.71 6.32P, 2.60 2.70 0.35 1.38Al
2O
3Surplus surplus surplus surplus bulk density, g/ml 0.930 0.952 0.870 0.897 mechanical strength, N/mm
*19.6 18.9 17.6 8.3* φ 1.0mm strips
Table 4 feedstock oil character feedstock oil triumph VGO proportion d (20 ℃), g/ml 0.903 sulphur, w% 0.46 nitrogen, w% 0.12 condensation point, ℃ 36 carbon residues, w% 0.05 boiling range, ℃ IBP/10% 2,90/,349 30%/50% 375/39270%/90% 406/43695%/EBP 446/467
Table 5 reaction process condition reaction pressure, MPa 6.37LHSV, h
-11.00 hydrogen/oil volume is than 1,000
The hydrodenitrogeneration reactivity of each routine catalyst of table 6 is catalyst embodiment 8 embodiment 9 comparative examples 3 comparative examples 4 reaction temperatures relatively, and ℃ 380 372 393 379
Claims (2)
1. a catalyst impregnating solution contains Mo, Ni, Co, P component, it is characterized in that in said Mo, Ni, Co, the P solution, every 100ml solution contains 45-80g MoO
3, 8-20g NiO, 0-15gCoO, P/MoO
3Weight ratio is 0.08-0.18.
2. the compound method of a catalyst impregnating solution is characterized in that said Mo, Ni, Co, P solution prepares as follows, and: a. adds molybdenum oxide and is heated to little boiling in the phosphate aqueous solution and makes it all or most of dissolving, is cooled to 60-70 ℃; B. in a solution, add basic nickel carbonate, be heated to little boiling and make its dissolving; C. in b solution, add nickel nitrate and/or cobalt nitrate; D. heating evaporation concentrated solution c.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96109048 CN1057941C (en) | 1996-08-02 | 1996-08-02 | Catalyst maceration extract and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96109048 CN1057941C (en) | 1996-08-02 | 1996-08-02 | Catalyst maceration extract and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1172692A true CN1172692A (en) | 1998-02-11 |
| CN1057941C CN1057941C (en) | 2000-11-01 |
Family
ID=5120179
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96109048 Expired - Lifetime CN1057941C (en) | 1996-08-02 | 1996-08-02 | Catalyst maceration extract and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1057941C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1099902C (en) * | 1999-12-08 | 2003-01-29 | 中国科学院山西煤炭化学研究所 | Catalyst for treating SO2 in waste gas and its application method |
| WO2011029716A2 (en) | 2009-09-10 | 2011-03-17 | Albemarle Europe Sprl | Concentrated solutions comprising group vi metal, group viii metal, and phosphorus |
| EP2470300A2 (en) * | 2009-08-24 | 2012-07-04 | Albemarle Europe Sprl. | Solutions and catalysts comprising group vi metal, group viii metal, phosphorous and an additive |
| WO2018161949A1 (en) * | 2017-03-09 | 2018-09-13 | 武汉凯迪工程技术研究总院有限公司 | Hydrotreating catalyst impregnating solution and preparation method therefor |
| WO2018161952A1 (en) * | 2017-03-09 | 2018-09-13 | 武汉凯迪工程技术研究总院有限公司 | Method for preparing hydrotreating catalyst by impregnation method |
-
1996
- 1996-08-02 CN CN 96109048 patent/CN1057941C/en not_active Expired - Lifetime
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1099902C (en) * | 1999-12-08 | 2003-01-29 | 中国科学院山西煤炭化学研究所 | Catalyst for treating SO2 in waste gas and its application method |
| EP2470300B1 (en) * | 2009-08-24 | 2022-10-05 | Albemarle Europe Sprl. | Solutions and catalysts comprising group vi metal, group viii metal, phosphorous and an additive |
| US10173201B2 (en) | 2009-08-24 | 2019-01-08 | Albemarle Europe Sprl | Solutions and catalysts comprising group VI metal, group VIII metal, phosphorus and an additive |
| US9254478B2 (en) | 2009-08-24 | 2016-02-09 | Albemarle Corporation | Solutions and catalysts comprising group VI metal, group VIII metal, phosphorus and an additive |
| EP2470300A2 (en) * | 2009-08-24 | 2012-07-04 | Albemarle Europe Sprl. | Solutions and catalysts comprising group vi metal, group viii metal, phosphorous and an additive |
| CN102497928B (en) * | 2009-09-10 | 2015-05-20 | 阿尔比马尔欧洲有限公司 | Concentrated solutions comprising group VI metal, group VIII metal, and phosphorus |
| AU2010294405B2 (en) * | 2009-09-10 | 2014-10-09 | Albemarle Europe Sprl | Concentrated solutions comprising group VI metal, group VIII metal, and phosphorus |
| CN102497928A (en) * | 2009-09-10 | 2012-06-13 | 阿尔比马尔欧洲有限公司 | Concentrated solutions comprising group VI metal, group VIII metal, and phosphorus |
| US9364816B2 (en) | 2009-09-10 | 2016-06-14 | Albemarle Europe Sprl | Concentrated solutions comprising group VI metal, group VII metal, and phosphorus |
| WO2011029716A3 (en) * | 2009-09-10 | 2011-06-30 | Albemarle Europe Sprl | Concentrated solutions comprising group vi metal, group viii metal, and phosphorus |
| EP3821978A1 (en) | 2009-09-10 | 2021-05-19 | Albemarle Europe Sprl. | Process for forming a catalyst with concentrated solutions comprising group vi metal, group viii metal, and phosphorus |
| WO2011029716A2 (en) | 2009-09-10 | 2011-03-17 | Albemarle Europe Sprl | Concentrated solutions comprising group vi metal, group viii metal, and phosphorus |
| WO2018161949A1 (en) * | 2017-03-09 | 2018-09-13 | 武汉凯迪工程技术研究总院有限公司 | Hydrotreating catalyst impregnating solution and preparation method therefor |
| WO2018161952A1 (en) * | 2017-03-09 | 2018-09-13 | 武汉凯迪工程技术研究总院有限公司 | Method for preparing hydrotreating catalyst by impregnation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1057941C (en) | 2000-11-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0359356B1 (en) | A method of presulfiding a hydrotreating catalyst | |
| US4255282A (en) | Hydrotreating catalyst and process for its preparation | |
| RU2313392C1 (en) | Diesel fraction hydrodesulfurization catalyst and a method for preparation thereof | |
| CA2545328A1 (en) | Hydroconversion catalysts and methods of making and using same | |
| CN1916120A (en) | Hydrotreating catalyst for bad heavy distillate, and preparation method | |
| RU2534997C1 (en) | Method of preparing catalyst for hydropurification of hydrocarbon raw material | |
| CN101733131A (en) | Metal sulfide catalyst for hydrogenation treatment of fuel oil | |
| US3686137A (en) | Sulfide precipitated catalysts | |
| CN104437578B (en) | Hydrodesulfurization catalyst, preparation method and applications thereof | |
| CN1172692A (en) | Catalyst maceration extract and its preparation method | |
| CN1506163A (en) | Aluminia carrier and hydrogenating catalyst with the carrier | |
| CN1053459C (en) | Preparation method of hydrotreating catalyst | |
| RU2724613C1 (en) | Hydrotreating method of diesel fuel | |
| CN85103891A (en) | The preparation method of the hydrogenation conversion catalyst on the carrier and the catalyst for preparing in this way | |
| CN101590416A (en) | Molybdenum-nickel hydrogenation catalyst and preparation method thereof | |
| EA038249B1 (en) | Catalyst for hydrotreatment of hydrocracking feedstocks | |
| JP4047044B2 (en) | Heavy oil hydrodesulfurization catalyst, method for producing the same, and hydrodesulfurization method for heavy oil | |
| RU2387475C1 (en) | Catalyst, method of preparing said catalyst and process for hydrofining hydrocarbon material | |
| CN101058074A (en) | Heavy fractional oil hydrogenation treating catalysts | |
| CN1105053A (en) | Fine catalyst produced by fraction oil hydrogenation | |
| JPH02214544A (en) | Catalyst for hydrocracking of heavy oils | |
| CN108940357A (en) | The Hydrobon catalyst and the preparation method and application thereof of mesoporous ETS-10 Zeolite support | |
| CN1102643C (en) | Catalyst for hydrorefining pertroleum wax and its preparing process | |
| CN1098913C (en) | Hydrogenating catalyst and its preparing process | |
| CN1107702C (en) | Hydrogenation catalyst and its producing process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: CHINA PETROCHEMICAL CORPORATION; CHINA PETROLEUM & Free format text: FORMER NAME OR ADDRESS: CHINA PETRO-CHEMICAL CORP.; FUSHUN PETROCHEMICAL INSTITUTE., CHINA PETROCHEMICAL CORP. |
|
| CP01 | Change in the name or title of a patent holder |
Patentee after: China Petrochemical Group Corp. Patentee after: Sinopec Group Fushun Research Institute of Petroleum and Petrochemicals Patentee before: China Petrochemical Corporation Patentee before: Fushun Research Inst. of Petroleum Processing, China Petro-chem. Corp. |
|
| CX01 | Expiry of patent term |
Granted publication date: 20001101 |
|
| EXPY | Termination of patent right or utility model |