CN102041050A - Operation method of vulcanized catalyst - Google Patents
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Abstract
The invention relates to an operation method of a vulcanized catalyst, which comprises steps of loading the vulcanized catalyst into a reactor, introducing inert gas to replace air in the reactor and air in pipes in front of and behind the reactor, gradually raising the temperature to the activation temperature, switching hydrogen, adjusting pressure and temperature to reaction pressure and reaction temperature after airflow is stable, and introducing raw oil to carry out hydrogenation reaction, wherein a sulfide precursor containing metal Mo or W, Ni or Co, and a catalyst carrier required by the dipping of the dipping solution of an organic assistant are adopted by the vulcanized catalyst, and can be dried to obtain the vulcanized catalyst. The operation method solves the disadvantages of high preparation cost, long prevulcanization time and high operating cost of the traditional oxidation state catalyst. The catalyst prepared by the method does not need to be pre-vulcanized, and the preparation process and the operation method are simple, and are suitable for preparing the petroleum distillate hydrogenation catalyst. The hydrogenation activity of the catalyst prepared by the operation method is better than that of the traditional catalyst.
Description
Technical field
The present invention relates to a kind of start-up method of sulfide type catalyst, particularly use the start-up method of the formulations prepared from solutions sulfurized hydrogenation catalyst that contains the metallic sulfide presoma.
Background technology
Conventional hydrogenation catalyst is an oxidation state, and the material that really plays active function during actual the use is sulphided state, so need vulcanize in reactor before use.Method for pre-sulphuration in a kind of typical device has been described among the patent CN1171430A, wherein vulcanizing agent is selected dithiocarbonic anhydride or dimethyl disulfide etc. for use, the volume ratio of vulcanizing agent gas and catalyzer is generally 300～600, sulfuration is carried out under normal pressure or high pressure, general intensification and constant temperature program are to vulcanize 2～6 hours down at 200～240 ℃, again 320～360 ℃ of sulfurations 8～12 hours.This has not only increased production cost, and sulfidation pollutes human and environment easily, and therefore scientific research personnel both domestic and external actively seeks redress.Present research is mainly concentrated both ways: being the outer prevulcanized of device on the one hand, is directly to prepare sulfide type catalyst on the other hand.The outer prevulcanized of device is meant adopts the method for distillation, fusion or dipping vulcanizing agent to be introduced in the hole of oxidized catalyst, in the presence of rare gas element, make the catalyst member prevulcanized then through hyperthermic treatment, at last catalyzer is packed in the reactor, in the presence of hydrogen, finish the final prevulcanized of catalyzer.The research of the outer prevulcanized of device is comparatively deep, and relevant report is also more, as the outer method for pre-sulphuration of EPRES hydrogenating catalyst of Fushun Petrochemical Research Institute etc.Vulcanize in the outer pre-curing technology of device and the device and compare, has the catalyst activity height, save on-stream time, simplify the step that goes into operation, human and environment is polluted advantages such as little, but the outer prevulcanized of device is the same with prevulcanized in the device, under the hydrogen effect, hydrogenolysis may appear in oxidized catalyst in the pre-vulcanization process, and active ingredient and carrier bonding force are often too strong, make hydrogenation catalyst do not caused activity of such catalysts further not improve by complete cure.Catalyzer increases the production stage of catalyzer through oxidation state prevulcanized use again, and production cost strengthens, and directly influences the economy of technology.So various countries very pay attention to the research of direct preparation sulfide type catalyst.
US4,528,089 have introduced the preparation method of a kind of hydrogenating desulfurization and hydrodenitrogenation catalyst, are raw material with ammonium thiomolybdate or alkyl ammonium thiomolybdate, and reaction obtains powder catalyst in the presence of the hydrogen in enclosed autoclave.US4,650,563 earlier with inorganic salt and the ammonium thiomolybdate and the quadrol mixing of nickel or cobalt, and reaction under certain condition generates mixture, and reaction obtains required catalyzer in containing the hydrogen of hydrogen sulfide then.US7,132,386 have reported a kind of method for preparing cobalt molybdenum sulfide type catalyst, ammonium thiomolybdate, cobalt chloride and alkyl ammonia bromide are mixed generating intermediate product earlier, it are moved in the reactor again, at 300 ℃, 500psi hydrogen pressure reaction down generates MoS
2And Co
9S
8US6,451,729 are dissolved in ammonium thiomolybdate in the organic solvent, produce the non-loading type MoS of high-ratio surface in the presence of high-temperature hydrogen
2Catalyzer, the hydrogenation cracking activity height of this catalyzer.CN1569331A discloses a kind of modification cobalt molybdenum base sulfide catalyst and preparation method thereof, by preparation ammonium thiomolybdate solution, and co-precipitation molybdenum, cobalt and the third transition metal constituent element, roasting under nitrogen protection makes black powder shape catalyzer.The deficiency of above technology is that catalyzer needs roasting in protection gas, the preparation cost height, and can only prepare powder catalyst, can not be used for large-scale hydrogenation unit.The technical process complexity, the tooling cost height.
CN1557917A discloses a kind of sulfurized hydrogenation catalyst and preparation method thereof; this Preparation of catalysts method mainly is that the carrier of conventional catalyst is incorporated into the presoma of group vib metal M o and W in the hole of catalyst carrier for hydrgenating by adopting solubility Thiomolybdate and thiqtung state solution; 350 ℃ of roastings are 4 hours under nitrogen protection; again with containing Ni; the solution impregnation of Co; 350 ℃ of roastings are 4 hours under nitrogen protection, thus the loading type sulfide catalyst of preparation Mo, W, Co, Ni.The shortcoming of this patent is that catalyzer needs roasting in protection gas, tooling cost height.And elder generation forms MoS
2And WS
2The back forms NiS and CoS, is unfavorable for forming the active phase of Co-Mo (W)-S or Ni-Mo (W)-S, influences the hydrogenation activity of catalyzer.
In sum, the sulfide type catalyst technology of preparing that present document is reported, catalyst preparation process needs rare gas element or hydrogen shield; the technical process complexity; the tooling cost height can not be used for large-scale hydrogenation unit, and the hydrogenation activity of catalyzer is still waiting to improve.And document scheme that goes into operation of not mentioned sulfide type catalyst all.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of start-up method of sulfide type catalyst.The catalyzer that uses in the process that goes into operation is to adopt the formulations prepared from solutions sulfide type catalyst that contains the sulfide presoma, and the sulfide type catalyst preparation method is simple, and preparation process does not need protection of inert gas.Be easy to form the active phase of two high classes of catalytic activity, catalyzer use properties height.Start-up method is simple, does not need prevulcanized, and the concentrated heat release in the reactivation process can be effectively controlled in activation in the presence of rare gas element, directly carries out hydrogenation reaction behind the importing hydrogen.
The start-up method of sulfide type catalyst of the present invention comprises following content:
1) sulfide type catalyst is packed in the reactor;
2) feed the air that reaches in rare gas element such as the nitrogen replacement reactor in the pipeline of reactor front and back, progressively be warming up to activation temperature, system pressure can be any pressure that reactor can bear;
3) switch hydrogen, treat to adjust pressure and temperature to reaction pressure and temperature of reaction behind the steady air current, advance stock oil and begin to carry out hydrogenation reaction.
Described sulfide type catalyst adopts following method preparation:
1) chooses suitable alumina supporter, the pore volume＞0.4ml/g of carrier, specific surface＞150m
2/ g;
2) preparation contains the dipping solution of sulfide presoma, Ni or Co inorganic salt and the organic additive of metal M o or W.The concentration of dipping solution is determined according to the demand of active ingredient in the preparation catalyzer, as wherein containing molybdenum component (in molybdic oxide) 15～45g in every 100ml steeping fluid, nickel component (in nickel oxide) 3～8g.
3) use this solution impregnated catalyst carrier, drying promptly gets sulfide type catalyst then.
Among the sulfide type catalyst preparation method of the present invention, the sulfide presoma of metal M o or W comprises Thiomolybdate or thiqtung state, is preferably ammonium salt.Thiomolybdate can comprise the alkyl Thiomolybdate, thiqtung state can comprise the alkyl thiqtung state, the alkyl of alkyl Thiomolybdate and alkyl thiqtung state can be saturated hydrocarbyl such as alkyl, cycloalkyl etc., also can be unsaturated alkyl such as alkene, the carbonatoms of alkyl is generally 1～100, is preferably 2～20.The metallic sulfide presoma can be selected commerical prod, also can prepare by this area ordinary method.
Organic additive can be to have material various and metal Ni or Co inorganic salt generation complex reaction now, as aminocarboxylic acids material, and organic phosphine acids material etc.The organic additive consumption is determined according to the consumption of the inorganic salt of metal Ni or Co, generally more than theoretical consumption (theoretical complex reaction consumption), is generally theoretical consumption and gets final product for 1～1.5 times.The inorganic salt of Ni or Co can be any soluble inorganic salt, are preferably nitrate or the carbonate of Ni or Co.During the dipping solution preparation, elder generation is with inorganic salt and the organic additive wiring solution-forming of Ni or Co, mix with the sulfide precursor solution of metal M o or W then, or directly the sulfide presoma of metal M o or W is dissolved in the inorganic salt of Ni or Co and the solution that organic additive is made into.Also can prepare the inorganic salt and the solution of organic additive and the sulfide precursor solution of metal M o or W that contain Ni or Co respectively, carry out step impregnation.The service requirements that the concrete kind of Mo, W, Ni, Co and content are pressed catalyzer in the sulfide type catalyst determines that total metal counts 10%～40% with oxide weight in the general catalyzer.The auxiliary agent that can contain this area routine in the sulfide type catalyst is as P, Si, F, B, Ti, Zr etc.
In the preparation process of vulcanized catalyst of the present invention, described drying is conventional drying conditions, and as being lower than under 200 ℃ of conditions dry 1～10 hour, drying temperature is generally 20～180 ℃.Described drying can adopt protection of inert gas, also can not need protection of inert gas.
The step 2 that goes into operation of sulfide type catalyst of the present invention) in, activation temperature is generally 200～400 ℃ by the existence decision of reactive metal in the catalyzer, and the time is 1～10h; System pressure can be a normal pressure, the pressure that the reaction pressure of hydrogenation reaction or any reactor can bear.
Sulfide type catalyst goes into operation in the step 3), and hydrogenation conditions such as reaction pressure, temperature, hydrogen-oil ratio and air speed etc. are determined by those skilled in the art according to raw material oil properties, purpose product requirement and the catalyst performance of reaction.General reaction pressure is 1.0～20.0MPa, 200～400 ℃ of temperature, hydrogen-oil ratio 200～2000, air speed 1.0～10.0h
-1Described stock oil can be various raw materials that can hydrogenation and composition thereof.
The present invention adopts dipping solution that pickling process will contain sulfide presoma, Ni or Co inorganic salt and the organic additive of metal M o or W to load to prepare sulfide type catalyst on the support of the catalyst, and hydrogenation reaction is then carried out in activation in the presence of rare gas element.The inventive method has following advantage compared with prior art:
1) catalyzer is without oxidation state, and production technique is simple, and the Preparation of Catalyst cost is low;
2) group vib metal and group VIII metal flood simultaneously, are easy to generate the active phase (theory is thought the mixture of group vib metallic sulfide and group VIII metallic sulfide) of highly active two classes;
3) catalyzer heats up in the presence of rare gas element and goes into operation, and reduces the concentrated exothermic phenomenon in the process that goes into operation, and keeps reaction bed temperature even, prevents the generation of temperature runaway phenomenon.
4) catalyzer does not need prevulcanized, saves on-stream time, and is environmentally friendly;
5) the catalyzer use properties further improves.
Embodiment
In the sulfide type catalyst preparation process of the present invention, described pickling process is this area ordinary method, as required metal-salt is dissolved in the appropriate pH value aqueous solution, adopts saturated dipping or excessive impregnating mode to flood then and gets final product.
A kind of concrete preparation method is as follows for sulfide type catalyst of the present invention:
1, the preparation of support of the catalyst: adopt ordinary method to prepare support of the catalyst, how much select bearer type,, add the silicon oxide of auxiliary agent, add the aluminum oxide of auxiliary agent as sial according to the acidic site that catalyzer is required, or molecular sieve etc.The carrier powder is mixed with binding agent, expanding agent, extrusion aid, extrusion on banded extruder, support of the catalyst is made in drying, roasting.The content that support of the catalyst preparation method is well known to those skilled in the art.
2, the configuration of steeping fluid: with the sulfide presoma of group vib metal M o and W and inorganic salt and the organic additive wiring solution-forming of group VIII metal Ni or Co.
3, adopt steeping fluid impregnation catalyst agent carrier: adopt pickling process that steeping fluid is loaded on the support of the catalyst, and descended dry 1～10 hour, promptly get sulfide type catalyst at 20 ℃～200 ℃.
The technical characterstic that the invention is further illustrated by the following examples, but these embodiment can not limit the present invention.
Embodiment 1
A) preparation of sulfide type catalyst A
(the Shandong alumina producer is produced to take by weighing pseudo-boehmite, butt is 73% by weight) 900g, sesbania powder 19g, citric acid 32g, nitric acid (weight concentration 30%) 48ml, silica gel (containing silicon-dioxide 30% by weight) 159ml, deionized water 250ml mixes, be extruded into 1.2mm trifolium bar on banded extruder, dry back promptly gets required support of the catalyst 1 600 ℃ of roastings 3 hours.
Get Xiao Suangu and ATMP (Amino Trimethylene Phosphonic Acid) be dissolved in the deionized water clear solution, get tetraethyl-ammonium thiomolybdate solution and mix wiring solution-forming with it, amount of active ingredients is determined according to table 1 data in the solution.Get mixing solutions and spray carrier 1, promptly got catalyst A in 3 hours in 120 ℃ of dryings, Main physical character sees Table 1.
B) catalyzer start-up method and evaluation
Directly be warming up to 350 ℃ after the reactor that catalyzer is housed imports nitrogen, constant temperature 2 hours changes to hydrogen, adjusts reaction pressure to 6.0MPa, introduces stock oil and carries out hydrogenation reaction.Operational condition is: pressure 6.0MPa, air speed 2.0,350 ℃ of temperature, hydrogen-oil ratio 1000.Evaluation result sees Table 2.
Embodiment 2
A) preparation of sulfide type catalyst B
Get nickelous nitrate and nitrilotriacetic acid be dissolved in the deionized water clear solution, then ammonium thiomolybdate is dissolved in this solution and is made into dipping solution, amount of active ingredients is determined according to table 1 data in the dipping solution.Get dipping solution sprayed carrier 1, promptly got catalyst B in 3 hours in 120 ℃ of dryings, Main physical character sees Table 1.
B) catalyzer start-up method and evaluation are identical with embodiment 1.Evaluation result sees Table 2.
Embodiment 3
A) preparation of sulfide type catalyst C
Get nickelous nitrate and ethylenediamine tetraacetic acid (EDTA) be dissolved in the ammoniacal liquor clear solution, with ammonium thiomolybdate solution and sulfo-ammonium tungstate mixings wiring solution-forming, amount of active ingredients is definite according to table 1 data in the solution.Get mixing solutions and spray carrier 1, promptly got catalyzer C in 3 hours in 120 ℃ of dryings, Main physical character sees Table 1.
B) catalyzer start-up method and evaluation
Directly be warming up to 380 ℃ after the reactor that catalyzer is housed imports nitrogen, constant temperature 1 hour changes to hydrogen, adjusts reaction pressure to 6.0MPa, and temperature of reaction is reduced to 350 ℃, introduces stock oil and carries out hydrogenation reaction.Operational condition is identical with embodiment 1.Evaluation result sees Table 2.
Comparative example 1
A) preparation of oxidation catalyst D
Take by weighing molybdenum oxide and basic nickel carbonate, add deionized water and mix, add 85% phosphoric acid again, be heated to 75 ℃, constant temperature one hour obtains deep green clear solution, add metatungstic acid amine again and stir, promptly get steeping fluid after the dissolving, amount of active ingredients is determined according to table 1 data in the solution.Press water-intake rate 74ml/100g spray impregnated carrier A, 120 ℃ of dryings 3 hours dry sample, 500 ℃ of roastings 3 hours, catalyzer D, Main physical character sees Table 1.
B) catalyzer start-up method and evaluation
Oxidation catalyst is packed in the hydrogenator, after importing hydrogen, the reactor that catalyzer is housed directly is warming up to 120 ℃, advance vulcanized oil (for the mixture of boat coal and dithiocarbonic anhydride), rising to 350 ℃ subsequently carries out prevulcanized, is adjusted to reaction conditions behind the constant temperature 3h.Operational condition is: pressure 6.0MPa, air speed 2.0,350 ℃ of temperature, hydrogen-oil ratio 1000.Evaluation result sees Table 2.
Every physical properties of table 1 carrier and catalyzer
The hydrogenation activity evaluation result of table 2 catalyzer
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| Catalyzer | A | B | C | D |
| 20 ℃ of density, g/cm 3 | 0.848 | 0.851 | 0.847 | 0.853 |
| Cetane value | 49.9 | 50.7 | 52.4 | 47.1 |
| Desulfurization degree, % | 98.7 | 99.5 | 99.8 | 94.3 |
| Denitrification percent, % | ＞98.3 | ＞98.3 | ＞98.3 | ＞98.3 |
Claims (10)
1. the start-up method of a sulfide type catalyst comprises following content:
1) sulfide type catalyst is packed in the reactor;
2) feed the air that reaches in the inert gas replacement reactor in the pipeline of reactor front and back, progressively be warming up to activation temperature, system pressure can be any pressure that reactor can bear;
3) switch hydrogen, treat to adjust pressure and temperature to reaction pressure and temperature of reaction behind the steady air current, advance stock oil and begin to carry out hydrogenation reaction;
Described sulfide type catalyst adopts following method preparation:
1) chooses alumina supporter;
2) preparation contains the dipping solution of sulfide presoma, Ni or Co inorganic salt and the organic additive of metal M o or W; Or preparation contains inorganic salt and the solution of organic additive and the sulfide precursor solution of metal M o or W of Ni or Co respectively;
3) use this solution impregnated catalyst carrier, drying promptly gets sulfide type catalyst then.
2. it is characterized in that in accordance with the method for claim 1: described rare gas element is a nitrogen.
3. in accordance with the method for claim 1, it is characterized in that: step 2 goes into operation) in catalyzer in activation temperature be 200～400 ℃, the time is 1～10h; System pressure is a normal pressure, or any reactor pressure that can bear.
4. in accordance with the method for claim 1, it is characterized in that: among the sulfide type catalyst preparation method, the pore volume＞0.4ml/g of the alumina supporter of choosing, specific surface＞150m
2/ g.
5. in accordance with the method for claim 1, it is characterized in that: among the sulfide type catalyst preparation method, the sulfide presoma of metal M o or W comprises Thiomolybdate or thiqtung state.
6. it is characterized in that in accordance with the method for claim 5: described Thiomolybdate or thiqtung state are ammonium salt.
7. in accordance with the method for claim 1, it is characterized in that: among the sulfide type catalyst preparation method, the described organic additive of step (2) is and the material of metal Ni or Co inorganic salt generation complex reaction, comprises aminocarboxylic acid or organic phospho acid.
8. in accordance with the method for claim 7, it is characterized in that: the organic additive consumption determines according to the consumption of the inorganic salt of metal Ni or Co, is 1～1.5 times of theoretical complex reaction consumption.
9. in accordance with the method for claim 1, it is characterized in that: in the preparation process of vulcanized catalyst, described drying is being lower than under 200 ℃ of conditions dry 1～10 hour.
10. in accordance with the method for claim 1, it is characterized in that: in the preparation process of vulcanized catalyst, during the dipping solution preparation, elder generation is with inorganic salt and the organic additive wiring solution-forming of Ni or Co, mix with the sulfide precursor solution of metal M o or W then, or directly the sulfide presoma of metal M o or W is dissolved in the inorganic salt of Ni or Co and the solution that organic additive is made into.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104593050A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Operating method for vulcanized hydrogenation catalyst |
| US9574141B2 (en) | 2012-11-03 | 2017-02-21 | China Petroleum & Chemical Corporation | Wet start-up method for hydrogenation unit, energy-saving hydrogenation process and hydrogenation apparatus |
| CN107999092A (en) * | 2016-10-31 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of sulfurized hydrogenation catalyst and preparation method thereof and gasoline hydrodesulfurizationmethod method |
| CN110527553A (en) * | 2019-09-30 | 2019-12-03 | 中化泉州石化有限公司 | A kind of temperature-rising method for saving residual hydrogenation on-stream time |
| CN111378489A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Startup method of hydrogenation device |
| CN111375428A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Process for preparing sulfurized hydrogenation catalyst |
Family Cites Families (3)
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| US7132386B2 (en) * | 2003-04-07 | 2006-11-07 | Board Of Regents, The University Of Texas System | Preparation of amorphous sulfide sieves |
| CN1294240C (en) * | 2004-07-06 | 2007-01-10 | 中国石油化工股份有限公司 | Depth hydrogenation treatment method of faulty gasoline |
| CN101279296A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Sulfuration type catalyst and preparation thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9574141B2 (en) | 2012-11-03 | 2017-02-21 | China Petroleum & Chemical Corporation | Wet start-up method for hydrogenation unit, energy-saving hydrogenation process and hydrogenation apparatus |
| CN104593050A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Operating method for vulcanized hydrogenation catalyst |
| CN104593050B (en) * | 2013-11-03 | 2016-08-17 | 中国石油化工股份有限公司 | The start-up method of sulfurized hydrogenation catalyst |
| CN107999092A (en) * | 2016-10-31 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of sulfurized hydrogenation catalyst and preparation method thereof and gasoline hydrodesulfurizationmethod method |
| CN111378489A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Startup method of hydrogenation device |
| CN111375428A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Process for preparing sulfurized hydrogenation catalyst |
| CN111378489B (en) * | 2018-12-28 | 2021-01-05 | 中国石油化工股份有限公司 | Startup method of hydrogenation device |
| CN110527553A (en) * | 2019-09-30 | 2019-12-03 | 中化泉州石化有限公司 | A kind of temperature-rising method for saving residual hydrogenation on-stream time |
| CN110527553B (en) * | 2019-09-30 | 2021-08-31 | 中化泉州石化有限公司 | Heating method for saving residual oil hydrogenation start-up time |
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