CN103394364B - Production method of bad oil hydro-modifying catalyst - Google Patents
Production method of bad oil hydro-modifying catalyst Download PDFInfo
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- CN103394364B CN103394364B CN201310370863.3A CN201310370863A CN103394364B CN 103394364 B CN103394364 B CN 103394364B CN 201310370863 A CN201310370863 A CN 201310370863A CN 103394364 B CN103394364 B CN 103394364B
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Abstract
The invention discloses a production method of a bad oil hydro-modifying catalyst. The preparation process of the production method is as follows: preparing materials, ball-milling, spray-drying, preparing mud into billet, drying, roasting, examining carrier, soaking catalyst, re-roasting, examining and packaging. The catalyst has good coking resistance, good hydrothermal stability and a good desulfurization denitrification effect for a hydrofinishing process of light coal tar fractions.
Description
Technical field
The present invention relates to a kind of production method of poor oil catalyst for hydro-upgrading.
Background technology
Along with the day by day exhaustion of fossil energy and the development of catalytic cracking technology, in order to improve the output of diesel oil, in feedstock oil, the method that the ratio of residual oil or heavy oil (being referred to as poor oil) is the common raising production of diesel oil adopting of current petroleum chemical industry is mixed in increase.Yet, along with the increase of poor oil ratio, cause sulphur in oil plant, nitrogen and arene content to increase, Cetane number reduces, storage stability variation.Meanwhile, environmental protection institution considers from diesel combustion pollution on the environment and harm, the indexs such as the density of diesel oil, sulphur nitrogen content, Cetane number has been proposed to stricter requirement.Therefore, adopt catalytic cracking technology to make condensed-nuclei aromatics open loop, the chain rupture in poor oil, thereby reduce density and the sulphur nitrogen content of diesel oil, improve significantly the Cetane number in product oil, become poor oil catalysis and split the key issue in technology.
High for arene content, nitrogen content is high, the hydrocracking process of easy coking, hydro carbons that oxygen content is high, require catalyst to there is good anti-coking performance, the good stability under high-temperature water thermal environment, hydrogenation activity high, to guarantee the operation reliably and with long-term of cracking unit.Poor oil catalyst for hydro-upgrading is the catalyst that a class is suitable for intermediate oil deep hydrogenation, mainly take porous ceramics as carrier, and adopting phosphorus, nickel, molybdenum, tungsten etc. is active component, by the method for dipping, processes.At present both at home and abroad the key technical indexes of high-quality poor oil catalyst for hydro-upgrading is: olefins hydrogenation rate is greater than 98%, hydrodesulfurization rate is greater than 95%, aromatic hydrogenation saturation factor is greater than 50%.
Research and application about poor oil hydrogenation catalyst is mainly after 2005 both at home and abroad, as US Patent No. 6872678 B2 have invented a kind of active catalyst containing additive, YiVI family and/or VIII family metal are catalyst, are applicable to the hydrocracking of light oil, gasoline, diesel oil or mineral lubricating oil.The ultra-low sulfur of Spain's exploitation and the catalyst of aromatics diesel, have good desulfurization, hydrogenation, cracking effect.France HeBP company of Poitiers university joint development a kind of at Al
2o
3on carrier, flood Ni, Mo, P as the catalyst of hydrocracking, for hydrocracking poor ignition quality fuel, also obtained good effect.
China National Petroleum Corporation (CNPC) combines the FCC diesel oil hydrofining catalyst patent of application with China University Of Petroleum Beijing, a kind of preparation method containing molecular sieve catalyst for intermediate oil Deep Hydrotreating is disclosed, this catalyst is specially adapted to the hydrotreatment of poor ignition quality fuel, and diesel oil after treatment can be used as the blend component of fine-quality diesel oil.
CK-1 and the CK-2 catalyst of China University Of Petroleum Beijing's exploitation, to make by alkyl aluminum or aluminum alkoxide Hydrolyze method the diaspore that purity is greater than 70%, after mixing, zeolite through cation exchange through high-temperature roasting, obtains carrier again, take phosphorus, nickel, molybdenum, zinc is active component, its hydrodesulfurization rate reaches 98 ~ 99%, denitrification percent is 91 ~ 92%, and Cetane number improves 11 ~ 13Ge unit, and diesel yield can reach 98 ~ 99%.
High pressure hydrocracking/the modifying catalyst of Fushun Petrochemical Research Institute's development and production, applies in the oil refining apparatus of Jing Duojia unit, proves the condensation point that can significantly reduce oil product, improves diesel yield.
To sum up, both at home and abroad to the research of poor oil hydrogenation catalyst and effect, all there is following deficiency in them:
The one, the gum level of coal tar light fraction is high, carbon residue amount is high, and easily coking in unifining process, loses activity catalyst and blocking catalyst bed, thereby require catalyst to have good anti-coking performance;
The 2nd, the oxygen content of coal tar light fraction is high, and the water yield that hydrogenation deoxidation produces is large, and in course of reaction, water partial pressure is high, requires catalyst to have good hydrothermal stability;
The 3rd, the sulfur content of coal tar light fraction reaches 0.4 ~ 0.8wt%, nitrogen content up to 0.6 ~ 1.5wt%;
The 4th, the arene content of coal tar light fraction is high, and particularly condensed-nuclei aromatics content is high.
Summary of the invention
Hydrogenation of olefins, aromatic hydrogenation, hydrodesulfurization, hydrodenitrogeneration and the partial cracking of poor oil catalyst for hydro-upgrading of the present invention high arene content poor oil between 100 ~ 530 ℃ mainly for normal pressure boiling range, to meet the hydrorefined application demand of coal tar wet goods poor oil.The deficiency existing according to domestic and international existing poor oil hydrogenation catalyst, it is low that the object of the invention is just to provide a kind of oxygen content, gum level, carbon residue amount, the preparation method of desulfurization, poor oil hydrogenation catalyst that denitrification effect is good.
Core of the present invention is: described production method comprises the following steps: (1) makes cat ceramic carrier: component by weight: aluminium hydrate powder 40-60 part, mullite powder 20-30 part, talcum powder 10-15 part, kaolin 15-20 part are that raw material packs grinding in ball grinder into, make the granularity of raw material after ball milling be less than 30 μ m, raw material after ball milling is sprayed dry, add again active carbon 10-20 part, after mud processed, be processed into base substrate, base substrate is porous onion shape, and base substrate is dried and made cat ceramic carrier by 500～750 ℃ of high-temperature roasting 3-4 hour; Base substrate of the present invention refers to the roasting under nitrogen protection 500～750 ℃ of high-temperature roastings, otherwise active carbon meeting ashing; (2) preparing metal catalyst soakage solution: component by weight: nickel nitrate 20-30 part, ammonium tetramolybdate 10-20 part, ammonium metatungstate 30-50 part add the water-soluble solution of 100-200 part after mixing, then the technical grade SPA 40-60 part that is 85% with concentration is mixed, and is mixed with metallic catalyst dipping solution; (3) utilize metallic catalyst dipping solution to soak into ceramic monolith: the steeper of the cat ceramic carrier that sinters and be up to the standards being put into vacuum-pumping, start vavuum pump, in container during reach-0.095MPa of vacuum, open the inlet valve of catalyst soakage solution, utilize the automatic suction catalyst dipping solution of negative pressure in steeper, keep closing vavuum pump after vacuum state dipping 30min, pass into atmosphere, when steeper internal pressure returns to normal pressure, open steeper, take out the product having flooded and drain; (4) roasting: the cat ceramic carrier draining after dipping is obtained to poor oil catalyst for hydro-upgrading for 4 ~ 6 hours 400 ~ 500 ℃ of roastings.
The invention has the advantages that the unifining process for coal tar light fraction, anti-coking performance and good hydrothermal stability, desulfurization removing nitric effect are high, hydrogenation of olefins and the high Ni-Mo-W of aromatic hydrogenation saturation factor are poor oil hydro-upgrading effective catalyst.
Specific embodiment
Component by weight: 20 parts of 40 parts of aluminium hydrate powders, 20 parts of mullite powders, 15 parts of talcum powder, kaolin pack grinding in ball grinder into for raw material, after ball milling, the granularity of raw material is 25 μ m, raw material after ball milling is sprayed dry, add again 15 parts of active carbons, after mud processed, be processed into base substrate, base substrate is porous onion shape, after base substrate is dried, under nitrogen protection, through 600 ℃ of high-temperature roastings, within 3.5 hours, makes cat ceramic carrier; Then component by weight: nickel nitrate (Ni (NO
3)
26H
2o) 25 parts, ammonium tetramolybdate ((NH
4)
2mo
4o
132H
2o) 15 parts, ammonium metatungstate ((NH
4)
2mo
4o
132H
2o) after 40 parts of mixing, add the water-soluble solution of 150 parts, 50 parts of technical grade SPAs that is then 85% with concentration mix, and are mixed with metallic catalyst dipping solution; The cat ceramic carrier that sinters and be up to the standards is put into the steeper of vacuum-pumping, start vavuum pump, in container during reach-0.095MPa of vacuum, open the inlet valve of catalyst soakage solution, utilize the automatic suction catalyst dipping solution of negative pressure in steeper, keep closing vavuum pump after vacuum state dipping 30min, pass into atmosphere, when steeper internal pressure returns to normal pressure, open steeper, take out the product having flooded and drain; (4) roasting: the cat ceramic carrier draining after dipping is obtained to poor oil catalyst for hydro-upgrading for 6 hours 500 ℃ of roastings.
The poor oil catalyst for hydro-upgrading product of this project development is on probation in the hydrogenation plant of Huhehaote petrochemical industry branch company of PetroChina Company Ltd., result shows that this catalyst is stable, product quality reaches all specification requirements of device and is better than like product, and user's application result is as shown in table 1.
Table 1
Table 2 be this Project Product in the trial state of Anshan, liaoning Province city petrochemical industry Co., Ltd diesel oil hydrogenation modification, prove that equally this product quality reaches all specification requirements of user.
Table 2
| Testing time | 2010-1-22 | 2012-5-4 |
| Chemical hydrogen consumption % | 2.1 | 2.12 |
| Liquids recovery rate % | 98.9 | 98.56 |
| Diesel oil distillate yield % | 77.26 | 76.94 |
| Diesel oil density kg/m after cut 3 | 868.8 | 869.0 |
| Sulfur content μ g/g | 16 | 33 |
| Nitrogen content μ g/g | 82 | 127 |
| Olefins hydrogenation rate % | 98.1 | 98.0 |
| Aromatic hydrogenation saturation factor % | 51.4 | 51.1 |
| Cracking rate % | 39.7 | 38.4 |
| Desulfurization degree % | 99.70 | 99.30 |
| Denitrification percent % | 98.75 | 98.36 |
Table 3 poor oil catalyst for hydro-upgrading main physical and chemical
Claims (1)
1. the production method of a poor oil catalyst for hydro-upgrading, it is characterized in that: described production method comprises the following steps: (1) makes cat ceramic carrier: component by weight: aluminium hydrate powder 40-60 part, mullite powder 20-30 part, talcum powder 10-15 part, kaolin 15-20 part is that raw material packs grinding in ball grinder into, make the granularity of raw material after ball milling be less than 30 μ m, raw material after ball milling is sprayed dry, add again active carbon 10-20 part, after mud processed, be processed into base substrate, base substrate is porous onion shape, after being dried, base substrate through 500～750 ℃ of high-temperature roasting 3-4 hour, makes cat ceramic carrier under nitrogen protection, (2) preparing metal catalyst soakage solution: component by weight: nickel nitrate 20-30 part, ammonium tetramolybdate 10-20 part, ammonium metatungstate 30-50 part add the water-soluble solution of 100-200 part after mixing, then the technical grade SPA 40-60 part that is 85% with concentration is mixed, and is mixed with metallic catalyst dipping solution, (3) utilize metallic catalyst dipping solution to soak into ceramic monolith: the steeper of the cat ceramic carrier that sinters and be up to the standards being put into vacuum-pumping, start vavuum pump, in container during reach-0.095MPa of vacuum, open the inlet valve of catalyst soakage solution, utilize the automatic suction catalyst dipping solution of negative pressure in steeper, keep closing vavuum pump after vacuum state dipping 30min, pass into atmosphere, when steeper internal pressure returns to normal pressure, open steeper, take out the product having flooded and drain, (4) roasting: the cat ceramic carrier draining after dipping is obtained to poor oil catalyst for hydro-upgrading for 4 ~ 6 hours 400 ~ 500 ℃ of roastings.
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| CN106582842A (en) * | 2016-12-14 | 2017-04-26 | 钦州学院 | Modification catalyst for inferior crude oil and preparation method of modification catalyst |
| CN115475622B (en) * | 2022-08-24 | 2023-08-25 | 宁波中金石化有限公司 | Preparation method and application of slurry bed hydrogenation catalyst based on waste porcelain powder carrier |
| CN115491232B (en) * | 2022-10-13 | 2024-01-23 | 陕西延长石油（集团）有限责任公司 | Method for producing ultralow-sulfur marine fuel oil by low-pressure hydrogenation of heavy inferior residual oil |
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Effective date of registration: 20160527 Address after: 337027 Jiangxi city of Pingxiang province Xiangdong District La Shi Zhen furnace Village (Industrial Park) Patentee after: Jiangxi city of Pingxiang Province in Eastern Petroleum Chemical Packing Factory Address before: 337027 Jiangxi city of Pingxiang province (LA city industrial zone in Jiangxi province to Pingxiang Xiangdong petrochemical packing factory) Patentee before: Duan Wenhui |
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