CN100360237C - A kind of preparation method of sulfurized hydrogenation catalyst - Google Patents
A kind of preparation method of sulfurized hydrogenation catalyst Download PDFInfo
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- CN100360237C CN100360237C CNB2005100464312A CN200510046431A CN100360237C CN 100360237 C CN100360237 C CN 100360237C CN B2005100464312 A CNB2005100464312 A CN B2005100464312A CN 200510046431 A CN200510046431 A CN 200510046431A CN 100360237 C CN100360237 C CN 100360237C
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Abstract
本发明涉及一种用于烃油加氢处理的硫化型催化剂制备方法，该种制备方法是，先担载一定分量的含有元素周期表中Ⅵ族和Ⅷ族金属的前身化合物，然后引入元素硫，经过一定热处理后再加入剩余量的含Ⅵ族和Ⅷ族金属的前身化合物，并干燥处理。本发明方法将催化剂的预硫化与催化剂制备过各有机结合，提高了催化剂的反应性能，该催化剂适用于烃油加氢处理过程，特别适用于轻质馏分油进行加氢脱硫反应、加氢脱氮反应以及芳烃的加氢饱和等催化反应过程。The invention relates to a method for preparing a sulfurized catalyst for hydrotreating hydrocarbon oil. The preparation method is as follows: a certain amount of precursor compounds containing metals of Group VI and Group VIII in the periodic table of elements are loaded first, and then elemental sulfur is introduced into the catalyst. After a certain heat treatment, the remaining amount of precursor compounds containing Group VI and Group VIII metals are added and dried. The method of the present invention organically combines the presulfurization of the catalyst with the preparation of the catalyst to improve the reaction performance of the catalyst. The catalyst is suitable for the hydroprocessing process of hydrocarbon oil, especially suitable for hydrodesulfurization reaction and hydrodehydrogenation of light distillate oil. Catalytic reaction processes such as nitrogen reaction and hydrogenation saturation of aromatic hydrocarbons.
Description
Technical field
The present invention relates to a kind of preparation method of high activity catalyst for hydrogenating hydrocarbon oil, with the oily needs of producing of the light ends that satisfies cleaning.
Background technology
Hydrogenation catalyst is used to handle that hydrocarbon ils carries out hydrodesulfurization, hydrodenitrogeneration under the condition that hydrogen exists, hydrogenation is saturated and reaction such as hydrocracking, hydrogenation catalyst is a carrier with the stronger inorganic oxide of adsorption capacity such as aluminium oxide, titanium oxide, silica and aluminium oxide and silica compound, VI family comprises metals such as Mo and/or W in the load periodic table of elements on carrier, metals such as Co of VIII family and/or Ni, these metals exist with oxide form.The oxide form catalyst activity is lower, changes into corresponding metal sulfide usually and just has higher activity, therefore must carry out presulfurization and handle after catalyst is packed hydrogenation plant into.When the reactive metal high degree of dispersion of sulphided state, catalyst just has high activity.
The method for pre-sulphuration of prior art, mainly comprise methods such as outer presulfurization of device and the interior presulfurization of device, these methods all are to add vulcanizing agent after Preparation of Catalyst is finished or the oxidation state reactive metal is converted into sulphided state, carry out certain processing then, preserve, transport and use with suitable.These methods are carried out the presulfurization of Preparation of Catalyst and catalyst respectively, both are not combined, and the serviceability of catalyst can also further be improved.As USP5017535, EP 329499, CN1107539C etc. promptly be Preparation of Catalyst is finished after, again sulphur-containing substance is loaded on the catalyst.
Start with in order to make catalyst obtain serviceability preferably, to have in the prior art from the Preparation of catalysts method.For example Japanese patent application publication No. 59-102442 and 59-69147 have mentioned a series of methods that prepare catalyst, according to said method, and with the reactive metal aqueous solution oxide impregnation alumina supporter that contains the carboxylic-acid substance, roasting then.Carboxylic acids thing such as citric acid, malic acid etc. form complex with reactive metal.To contain amino, cyano group organic compound in the European patent 0181035, as follows amion acetic acid, disodium salt or diethylenetriamines etc. add the aqueous solution of reactive metals, and the catalyst of making is dry under less than 200 ℃ temperature.Make activity of such catalysts metal dispersity height like this, activity of such catalysts can improve.Above-mentioned catalyst preparation process has just been added some auxiliary agents in the reactive metal dipping solution, improve the serviceability of catalyst to a certain extent, but directly Preparation of catalysts process and pre-vulcanization process is not combined.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of hydrogenization catalyst preparation method, the inventive method can obtain a kind of hydrogenation catalyst that contains vulcanizing agent, and preparation process is simple, and catalyst vulcanization is abundant, and is active high.
Hydrogenation catalyst preparation process of the present invention may further comprise the steps:
(1) get or prepare the catalyst intermediate that contains the partial hydrogenation reactive metal oxides, reactive metal oxides is 2%～85% of a final catalyst requirement, and is preferred 5%～70%, most preferably 25%～70%;
(2) catalyst intermediate that obtains in the step (1) is introduced elementary sulfur (being elemental sulfur);
(3) material that obtains of step (2) is heat-treated;
(4) the hydrogenation active metals component of dipping surplus is also dry, is finally contained the hydrogenation catalyst of vulcanizing agent.
Wherein the described hydrogenation active metals of step (1) generally is selected from one or more among W, Mo, Ni, the Co, and content can need to determine, generally count 1%～50% of catalyst weight with oxide by using.
When the described catalyst intermediate of step (2) is introduced elementary sulfur, introduce organic solvent before and in the step of one afterwards or a few step.The concrete grammar of introducing organic solvent and elementary sulfur (elemental sulfur) can adopt one of various possible modes in the prior art, loads to earlier on the catalyst as (1) elementary sulfur, floods organic solvent then; (2) elementary sulfur is dispersed in the organic solvent, is incorporated on the catalyst jointly then; (3) earlier organic solvent is impregnated on the catalyst, introduces elementary sulfur then; (4) earlier organic solvent is impregnated on the catalyst, mixes with the elementary sulfur pressed powder then.The elementary sulfur consumption is generally the total theoretical metal of catalyst and needs 30%～120%, preferred 80%～105% of sulfur content.Catalyst is theoretical need sulfur content to be that institute's metallic components is converted into sulfide (Co on the catalyst
9S
8, MoS
2, Ni
3S
2, WS
2) time need the amount of sulphur.The organic solution consumption can be generally 0.05%～50% of catalyst intermediate weight by this area general condition operation, and is preferred 1%～50%, and more preferably 2%～30%.Organic solvent can adopt operable all kinds of solvents in the Containing Sulfur agent catalyst preparation process, and those skilled in the art know these solvents.In some organic solvents commonly used such as hydrocarbon ils, oxygen-bearing organic matter, sulfurous organic compound, the itrogenous organic substance etc. one or more.Oxygen-bearing organic matter is preferably selected organic carboxylic ester, and itrogenous organic substance is preferably selected organic amine or organic amino compounds, and sulfurous organic compound is preferably selected organic polysulfide.Oxygen-bearing organic matter, itrogenous organic substance etc. also can be introduced before elementary sulfur is introduced catalyst intermediate, and consumption is 0.1～7 with total metal molar ratio.Hydrocarbon ils generally can be from the heavy end wet goods of various naphthas, gasoline, kerosene, diesel oil, white oil, lam-oil, lube base oil, straight run and decompression one or more, the hydrocarbon ils that obtains of secondary operations preferably, the above-mentioned hydrocarbon ils that obtains as technologies such as catalytic cracking, thermal cracking.Organic carboxylic ester can be the organic carboxylic ester that contains 6～60 carbon atoms, the preferred fat acid glyceride.As sesame oil, safflower seed oil, corn oil, cottonseed oil, peanut oil, rapeseed oil, soya-bean oil, walnut oil, coconut oil, olive oil, sunflower oil, lard, n-butyl acetate, 1-Methoxy-2-propyl acetate, 1, the 4-butanediol diacrylate, the cyclohexylenedinitrilotetraacetic acid isopropyl ester, hexa-methylene-1,6 vulcabond, triethyl phosphate, methyl phenylacetate, isobutyl phenylacetate, the terephthalic acid (TPA) dinonyl, repefral, diethyl phthalate, Methyl Salicylate, butyl p-hydroxybenzoate, and in similar other organic carboxylic ester etc. one or more.Hydrocarbon ils, organic carboxylic ester can be used alone, but also also mix together, and use its weight ratio can be 1: 10～10: 1 (hydrocarbon ils: organic carboxylic ester) if mix.Can add an amount of sulfurous organic compound in the organic solvent, as sulfone class material, thio-alcohol material, thiurams material, organic polysulfide etc. one or more.
The described heat treatment process of step (3) is to handle 1～40 hour down at 100～300 ℃, and heat treated can be an inert gas environment, also can be that oxygen content is the oxygen atmosphere that has of 0.1v%～30v%.Heat treated pressure can be that normal pressure is to 3MPa.
The described dipping residual metallic of step (4) method can adopt conventional dipping process, descends dry 1～30 hour at 80～200 ℃ then, obtains final catalyst prod.
(1) and/or (4) step process in can add the required auxiliary agent of catalyst, as phosphorus, boron, silicon, fluorine, titanium, zirconium etc., the auxiliary agent use amount can be as required determined by this area general knowledge.
Find after deliberation, in the Preparation of catalysts process, support certain component active metal component earlier, introduce elementary sulfur then, the component of load residual metallic again, the catalyst that obtains like this has good presulfurization effect, has good serviceability during application.The present invention mainly provides the method for preparing high activated catalyst, can satisfy the needs of the light ends oil production of cleaning, the present invention has solved the complicated and inadequate problem of sulfuration of the sulfidation that exists in early stage technology and the method for preparing catalyst through repeatedly experimental study.Introduce behind the vulcanizing agent through certain heat treatment, and follow-up dipping active metal component and dry the processing, these introduce the processing procedure behind the vulcanizing agent, make catalyst thermal discharge when using activation of Containing Sulfur agent few, and heat release is even in the activation process, has controlled concentrated heat release problem effectively.
The specific embodiment
Further specify the process of the inventive method below by specific embodiment, wherein Chang Gui technology contents can be determined according to general knowledge and needs by those skilled in the art, does not therefore limit the scope of the invention.
Embodiment 1
Hydrogenation catalyst A: with the gama-alumina is carrier, and reactive metal consists of: Mo content is with MoO
3The meter weight percentage is 23.7%, and Co content is 4.5% in the CoO weight percentage, and P content is with P
2O
5The meter weight percentage is 3.1%.(disregarding the composition of vulcanizing agent)
Contain the above-mentioned composition Preparation of catalysts of vulcanizing agent process:
Get 1000 gram gamma-aluminium oxide carriers, the carrier specific area is 296m
2/ g, pore volume 0.87ml/g, with 129 gram molybdenum trioxides, 56 gram cobalt carbonates, 30.6 gram 85% phosphoric acid and an amount of water are mixed with the 900ml aqueous solution, flood above-mentioned carrier, and dipping sample later makes catalyst intermediate 340 ℃ of dryings 4 hours, and Mo content is with MoO
3The meter weight percentage is 10%, and Co content is 2% in the CoO weight percentage, and P content is with P
2O
5The meter weight percentage is 1.5%.The mixed solvent of 91.2 gram lactic acid and 5 gram triethanolamines is incorporated on the above-mentioned catalyst intermediate of 250 grams, introduces the elementary sulfur powder then, and handled 10 hours at 150 ℃ of normal pressures.The elementary sulfur consumption is 105% of a final catalyst activity theoretical metal need sulfur content.With 117 gram molybdenum trioxides, 67 gram cobalt carbonates, 25.7 gram 85% phosphoric acid and an amount of water are mixed with the semi-finished product of 780ml solution impregnating catalyst at last, and 120 ℃ dry 5 hours down, make finished catalyst (numbering catalyst A).The feedstock oil of catalyst A activity rating is Kuwait's normal pressure diesel oil, is the main character about feedstock oil below.
Embodiment 2
Hydrogenation catalyst B: with the gama-alumina is carrier, and reactive metal consists of: Mo content is with MoO
3The meter weight percentage is 25.8%, and Co content is 4.9% in the CoO weight percentage, and P content is with P
2O
5The meter weight percentage is 3.5%.(disregarding the composition of vulcanizing agent)
Contain the above-mentioned composition Preparation of catalysts of vulcanizing agent process:
Get 1000 gram gamma-aluminium oxide carriers, the carrier specific area is 296m
2/ g, pore volume 0.87ml/g, with 129 gram molybdenum trioxides, 56 gram cobalt carbonates, 30.6 gram 85% phosphoric acid and an amount of water are mixed with the 1300ml aqueous solution, flood above-mentioned carrier, and dipping sample later makes catalyst intermediate 340 ℃ of dryings 4 hours, and Mo content is with MoO
3The meter weight percentage is 8.9%, and Co content is 1.7% in the CoO weight percentage, and P content is with P
2O
5The meter weight percentage is 1.1%.It is in 1: 5 the solvent that the elementary sulfur powder is dispersed in catalytic cracking diesel oil and rapeseed oil volume ratio, solvent load is 1 5% of a catalyst intermediate weight, the elementary sulfur consumption is theoretical 37% of the sulfur content that needs of final catalyst metals, handled 5 hours at 180 ℃ in obturator then, final pressure is 0.4MPa (gauge pressure).With 120 gram molybdenum trioxides, 70 gram cobalt carbonates, 26.5 gram 85% phosphoric acid and an amount of water are mixed with the semi-finished product of 650ml solution impregnating catalyst at last, and 110 ℃ dry 6 hours down, make finished catalyst (numbering catalyst B).The feedstock oil of catalyst B activity rating is Kuwait's normal pressure diesel oil, is the main character about feedstock oil below.
Embodiment 3
According to the method for embodiment 1, active metallic content is 15% (weight) of final catalyst activity tenor in the minimizing catalyst intermediate, and the elementary sulfur use amount is 80% of a theoretical requirement, and other presses embodiment 1 method, gets catalyst C.
Embodiment 4
Press the method for embodiment 2, active metallic content is 70% (weight) of final catalyst activity tenor in the increase catalyst intermediate, and the elementary sulfur use amount is 110% of a theoretical requirement, and other presses the method for embodiment 2, gets catalyst D.
Embodiment 5
Hydrogenation catalyst E, carrier γ-Al
2O
3, active metal W O
319.3wt%, MoO
36.7wt%, NiO 4.2wt%.(disregarding the composition of vulcanizing agent)
Get the carrier identical, earlier with the whole MoO of infusion process load with embodiment 2
3And NiO, to press the method for embodiment 2 then and introduce elementary sulfur and solvent, the consumption of elementary sulfur is theoretical 98% of sulfur content, the final impregnating method load WO of needing of final catalyst
3, get catalyst E.
Comparative example 1
Get the oxidized catalyst with embodiment 1 same composition, press method and the condition of introducing elementary sulfur among the embodiment 1, introduces identical sulphur and solvent (being that catalyst is introduced elementary sulfur at last), must catalyst F.
The character of table 1 Kuwait normal pressure diesel oil
| Proportion | 0.8504 |
| Sulfur content (wt%) | 1.623 |
| Nitrogen content (μ g/g) | 730 |
| Boiling range, (℃) | |
| Initial boiling point | 234 |
| 50% (v) distillates a little | 316 |
| The end point of distillation | 389 |
The process conditions of table 2 evaluation test
| Reaction pressure (MPa) | 3.0 |
| Liquid hourly space velocity (LHSV) (h -1) | 2 |
| Reaction temperature (℃) | 330 |
| Hydrogen to oil volume ratio (v) | 350 |
| The duration of runs (hr) | 100 |
The activity of catalyst sample is represented (is 100 with comparative example) with relative hydrodesulfurization rate with relative hydrodenitrogeneration rate, the results are shown in Table 3.
Table 3 embodiment and comparative example evaluating catalyst performance
| Catalyst | A | B | C | D | E | F |
| Relative desulfurization degree | 135 | 128 | 114 | 108 | 127 | 100 |
| Relative denitrification percent | 129 | 125 | 112 | 106 | 148 | 100 |
| Maximum bed temperature rise in the activation process, ℃ | 15 | 16 | 18 | 19 | 17 | 26 |
Claims (10)
1, a kind of preparation method of sulfurized hydrogenation catalyst may further comprise the steps:
(1) get or prepare the catalyst intermediate that contains the partial hydrogenation reactive metal oxides, reactive metal oxides is 2%～85% of a final catalyst requirement by weight;
(2) introduce elementary sulfur in the catalyst intermediate that in step (1), obtains;
(3) material that step (2) is obtained is heat-treated;
(4) dipping hydrogenation active metals component is also dry, is finally contained the hydrogenation catalyst of vulcanizing agent, and the amount of the hydrogenation active metals component of dipping is counted the amount of remaining hydrogenation active metals oxide with its oxide;
Wherein the described heat treatment process of step (3) is to handle 1～40 hour down at 100～300 ℃, and heat treatment is inert gas environment, or oxygen content is the oxygen atmosphere that has of 0.1v%～30v%, and heat treated pressure is that normal pressure is to 3MPa; The described drying of step (4) is following dry 1～30 hour at 80～200 ℃.
2, in accordance with the method for claim 1, it is characterized in that reactive metal oxides is 5%～70% of a final catalyst requirement in the described catalyst intermediate.
3, in accordance with the method for claim 1, it is characterized in that reactive metal oxides is 25%～70% of a final catalyst requirement in the described catalyst intermediate.
4, in accordance with the method for claim 1, it is characterized in that described hydrogenation active metals is selected from one or more among W, Mo, Ni, the Co.
When 5, in accordance with the method for claim 1, it is characterized in that the described catalyst intermediate of step (2) is introduced elementary sulfur, introduce organic solvent before and in the step of one afterwards or a few step.
6, in accordance with the method for claim 5, it is characterized in that the method for described catalyst intermediate introducing organic solvent of step (2) and elementary sulfur can adopt one of following manner, (1) elementary sulfur loads to earlier on the catalyst, floods organic solvent then; (2) elementary sulfur is dispersed in the organic solvent, is incorporated on the catalyst jointly then; (3) earlier organic solvent is impregnated on the catalyst, introduces elementary sulfur then.
7, in accordance with the method for claim 1, it is characterized in that the described elementary sulfur consumption of step (2) is that the total theoretical metal of catalyst needs 30%～120% of sulfur content.
8, in accordance with the method for claim 1, it is characterized in that the described elementary sulfur consumption of step (2) is that the total theoretical metal of catalyst needs 80%～105% of sulfur content.
9, in accordance with the method for claim 1, the method that it is characterized in that the described dipping hydrogenation active metals of step (4) component adopts conventional dipping process.
10,, it is characterized in that the consumption of organic solvent of the described introducing of step (2) is 0.05%～50% of a catalyst intermediate weight according to claim 5 or 6 described methods.
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| CNB2005100464312A CN100360237C (en) | 2005-05-12 | 2005-05-12 | A kind of preparation method of sulfurized hydrogenation catalyst |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100453180C (en) * | 2006-12-20 | 2009-01-21 | 中国科学院山西煤炭化学研究所 | A kind of presulfurization method of hydrogenation catalyst |
| CN101890383B (en) * | 2009-05-19 | 2012-08-29 | 中国石油化工股份有限公司 | Hydrodenitrogenation catalyst and application thereof |
| CN101890381B (en) * | 2009-05-19 | 2012-07-18 | 中国石油化工股份有限公司 | Hydrotreating guard catalyst and application thereof |
| CN102039147B (en) * | 2009-10-21 | 2012-08-29 | 中国石油化工股份有限公司 | Preparation method of vulcanized catalyst |
| CN103801334B (en) * | 2012-11-08 | 2016-01-06 | 中国石油化工股份有限公司 | A kind of preparation method of sulfurized hydrogenation catalyst |
| CN111744517B (en) * | 2019-03-29 | 2022-10-21 | 中国石油化工股份有限公司 | Hydrotreating catalyst and application thereof |
| CN111744515B (en) * | 2019-03-29 | 2022-10-21 | 中国石油化工股份有限公司 | Hydrotreating catalyst and application thereof |
| CN111744516B (en) * | 2019-03-29 | 2022-11-15 | 中国石油化工股份有限公司 | A kind of hydrotreating catalyst and its application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5139990A (en) * | 1988-07-29 | 1992-08-18 | Akzo Nv | Process for the preparation of a resulfided catalyst |
| CN1082591A (en) * | 1992-04-01 | 1994-02-23 | 欧洲催化剂加工公司 | The catalyst presulfurizing method of processing hydrocarbons |
| CN1243456A (en) * | 1997-01-21 | 2000-02-02 | 法国埃勒夫阿基坦勘探生产公司 | Method for pre-sulphuration of catalysts |
| CN1611577A (en) * | 2003-10-31 | 2005-05-04 | 中国石油化工股份有限公司 | Prevulcanizing method for hydrogenating catalyst |
-
2005
- 2005-05-12 CN CNB2005100464312A patent/CN100360237C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5139990A (en) * | 1988-07-29 | 1992-08-18 | Akzo Nv | Process for the preparation of a resulfided catalyst |
| CN1082591A (en) * | 1992-04-01 | 1994-02-23 | 欧洲催化剂加工公司 | The catalyst presulfurizing method of processing hydrocarbons |
| CN1243456A (en) * | 1997-01-21 | 2000-02-02 | 法国埃勒夫阿基坦勘探生产公司 | Method for pre-sulphuration of catalysts |
| CN1611577A (en) * | 2003-10-31 | 2005-05-04 | 中国石油化工股份有限公司 | Prevulcanizing method for hydrogenating catalyst |
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