CN102041043A - Method for processing vulcanized hydrogenation catalyst - Google Patents
Method for processing vulcanized hydrogenation catalyst Download PDFInfo
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Abstract
The invention relates to a method for processing a vulcanized hydrogenation catalyst, which comprises the following steps of: filling the vulcanized hydrogenation catalyst into a reactor, introducing hydrogen to directly raise the temperature and perform thermal treatment of the catalyst, and then adjusting the pressure and the temperature to the reaction pressure and the reaction temperature for hydrogenation reaction, wherein the vulcanized hydrogenation catalyst is introduced with active metals of required categories and number by adopting a dipping method, a vulcanizing agent is introduced before, after or when the active metals are introduced, and the final vulcanized hydrogenation catalyst is obtained by drying. The catalyst prepared by the method does not need pre-vulcanizing; the preparation process is simplified by organically combining a thermal treatment process and an activation process of the catalyst; the processing method is simple and suitable for preparation of petroleum fraction hydrogenation catalysts; and the hydrogenation activity of the prepared catalyst exceeds that of the conventional catalyst.
Description
Technical field
The present invention relates to a kind of start-up method of sulfurized hydrogenation catalyst, belong to the improvement of hydrogenation catalyst start-up method.
Background technology
Crude oil poor qualityization tendency is obvious day by day in the world wide in recent years, and sulphur nitrogen and aromaticity content increase day by day in the petroleum products, and various countries are also more and more higher to environmental protection requirement, and obviously more and more stricter environmental requirement and the contradiction between this reality are more sharp-pointed; Hydrogenation technique is one of effective means of producing the clean oil product, and wherein hydrogenation catalyst then is the gordian technique of this technology.
Hydrogenation catalyst generally is made up of the group VIII with hydrogenating function and group vib metal or metal oxide and carrier and auxiliary agent with certain acid function, wherein group VIII and group vib metal exist with oxide form, and the material that really plays active function during actual the use is the sulfide of above-mentioned metal, so hydrogenation catalyst need pass through prevulcanized before use.
Conventional catalyst vulcanization method is divided into two kinds: sulfuration method and the outer sulfuration method of device in the device.The sulfuration method is that oxidized catalyst is packed in the hydrogenator in the device, feeds hydrogen in reactor and vulcanizing agent carries out prevulcanized in temperature-rise period.A kind of typical method for pre-sulphuration 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.The shortcoming of this method is: curing time is long, sulfuration cost height, and vulcanizing agent toxicity is big, inflammable, easily to the people, environment is polluted.The outer sulfuration method of device is meant that the method that adopts distillation, fusion or dipping introduces vulcanizing agent in the space of catalyzer of oxidized form, 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 prevulcanized of catalyzer.Typical sulfurization technology has the actiCAT technology of CRI company, the Xpress technology of TRICAT company and the novel sulfurization technology of AKZO company etc.Vulcanize in the outer pre-curing technology of device and the device and compare, have obvious advantage: save on-stream time, the simplification step that goes into operation; Catalyzer carries out prevulcanized in factory, reduces the refinery equipment investment, human and environment is polluted little etc.But the outer prevulcanized of device is the same with prevulcanized in the device, and catalyzer need pass through oxidation state prevulcanized again, and this just causes production stage loaded down with trivial details, complicated process of preparation, and during consumption energy consumption, the problem that economy is relatively poor.And because the reactive force of metal oxide and carrier is strong excessively, in the catalyzer sulfuration of active ingredient incomplete, active ingredient can not play one's part to the full, and causes metal to waste.
Chinese patent CN1569331 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 shortcoming of this method 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.
Chinese patent CN1557917 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 metal M o of IVB family and W in the space 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 method is a complex process, the preparation cost height.
In sum, the sulfide type catalyst technology of preparing that present document is reported, the powder catalyst of preparation is unsuitable for extensive hydrogenation unit and uses.The supported catalyst preparation process needs nitrogen protection, complex process, and the preparation cost height is unfavorable for large-scale commercial production, 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 sulfurized hydrogenation catalyst.The used sulfurized hydrogenation catalyst of the present invention adopts pickling process to introduce the reactive metal of required kind and quantity, before introducing reactive metal, introduce vulcanizing agent afterwards or simultaneously, obtains through super-dry then.The catalyzer of the inventive method preparation does not need prevulcanized, and heat treatment process and reactivation process combination with catalyzer directly import hydrogen and carry out hydrogenation reaction.
The start-up method of sulfurized hydrogenation catalyst of the present invention comprises following content:
1) sulfurized hydrogenation catalyst is packed in the reactor;
2) feed the air that reaches in the hydrogen exchange reactor in the pipeline of reactor front and back, progressively be warming up to thermal treatment temp, system pressure can be any pressure that reactor can bear;
3) adjust pressure and temperature after the thermal treatment to reaction pressure and temperature of reaction, advance stock oil and begin to carry out hydrogenation reaction;
Described sulfurized hydrogenation catalyst adopts following method preparation:
1) chooses alumina supporter, the pore volume＞0.4ml/g of carrier, specific surface＞150m
2/ g;
2) introduce the reactive metal of required kind and quantity with pickling process, before introducing reactive metal, introduce vulcanizing agent afterwards or simultaneously;
3) drying promptly gets sulfurized hydrogenation catalyst then.
Vulcanizing agent of the present invention is one or more in water-soluble sulphide salt such as sodium sulphite, ammonium sulfide, hydrogen sulfide ammonium, thiocarbamide, dithiocar-bamate and the dithioglycol etc., is preferably ammonium sulfide or hydrogen sulfide ammonium.The consumption of vulcanizing agent is 1～5 times of the required sulfur content of active ingredient complete cure, is preferably 1～1.5 times.The required sulfur content of active ingredient complete cure is converted into sulfide (Co by active metal component
9S
8, MoS
2, Ni
3S
2, WS
2) time need the amount of sulphur.
In the sulfurized hydrogenation catalyst preparation process of the present invention, carry out drying treatment after introducing reactive metal and introducing the vulcanizing agent process, drying conditions be a drying 1～10 hour under 20～200 ℃.
The reactive metal that sulfurized hydrogenation catalyst of the present invention relates to is generally group VIII and group vib metal, and the consumption of reactive metal is determined according to concrete service requirements, is generally 5%～50% in oxide weight.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 impregnated carrier then.Group VIII and group vib metal-salt are generally ammonium molybdate, molybdenum oxide, nickelous nitrate, basic nickel carbonate, metatungstic acid amine, Xiao Suangu, cobaltous dihydroxycarbonate etc., difference according to required catalysis, be made into the solution of different concns and proportioning, character according to metal-salt, generally can prepare acidity or basic solution, acidic solution is phosphoric acid or citric acid, and the solvent of basic solution is generally ammonia soln, quadrol, thanomin etc.In conjunction with the wettability of carrier and solution, be made into the solution of different pH values, as Mo-Ni-P, Mo-Ni-NH
3H
2O solution.
The step 2 that goes into operation of sulfurized hydrogenation catalyst of the present invention) in, the thermal treatment temp of catalyzer is generally 200～400 ℃, 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.
Sulfurized hydrogenation 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 has following advantage compared with prior art:
1) catalyzer is without oxidation state, and the preparation method is simple, and heat treatment step organically combines with the reactivation process that goes into operation, and simplifies production technique, the economy height of catalyzer.
2) active ingredient is 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) start-up method is simple, does not need prevulcanized, directly carries out hydrogenation reaction in the presence of hydrogen after the thermal treatment, saves on-stream time, and is environmentally friendly;
4) the catalyzer use properties further improves.
Embodiment
The preparation method of sulfurized hydrogenation catalyst of the present invention can adopt following three kinds of detailed processes.
1, floods reactive metal earlier, handle with sulfur agent solution then.
(1) group VIII and IVB family metal inorganic salt are dissolved in acidity or basic solution, are made into the solution of desired concn;
(2) solution with step (1) preparation adopts saturated pickling process or excessive pickling process impregnation catalyst agent carrier, and following dry 1～10 hour at 20～200 ℃;
(3) adopt saturated pickling process or excessive pickling process impregnation steps (2) gained material with the vulcanizing agent aqueous solution; Can regulator solution pH value be 4～11, make vulcanization reaction complete;
(4) step (3) gained material was in 20～200 ℃ of dryings 1～10 hour.
2, flood vulcanizing agent, supported active metal then earlier.
(1) adopt saturated pickling process or excessive pickling process impregnation catalyst agent carrier with the vulcanizing agent aqueous solution, and following dry 1～10 hour at 20～200 ℃;
(2) group VIII and IVB family metal inorganic salt are dissolved in acidity or basic solution, are made into the solution of desired concn;
(3) adopt the gains of saturated pickling process or excessive pickling process impregnation steps (1) with step (2) prepared solution; Can regulator solution pH value be 4～11, make vulcanization reaction complete.
(4), step (3) gained material is following dry 1～10 hour at 20～200 ℃.
3, reactive metal and vulcanizing agent flood simultaneously.
(1) group VIII and IVB family metal inorganic salt are dissolved in acidity or basic solution, are made into the solution of desired concn and pH value;
(2) adopt saturated pickling process or excessive pickling process to spray the impregnation catalyst agent carrier jointly with step (1) prepared solution and the vulcanizing agent aqueous solution, following dry 1～10 hour at 20～200 ℃ then;
In the inventive method, the support of the catalyst that relates to can adopt this area ordinary method preparation on demand.As how much selecting bearer type,, add the silica alumina of auxiliary agent, molecular sieve etc. as sial according to the required acidic site of catalyzer.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 technical characterstic that the invention is further illustrated by the following examples, but these embodiment can not limit the present invention, and the percentage composition that relates to is a weight percentage.
Embodiment 1
A) preparation of support of the catalyst
(the Shandong alumina producer is produced to take by weighing pseudo-boehmite, butt is 73%) 900g, sesbania powder 19g, citric acid 32g, nitric acid (30%) 48ml, silica gel (containing silicon-dioxide 30%) 159ml, deionized water 250ml mixed, and is extruded into 1.2mm trifolium bar on banded extruder, 600 ℃ of roastings 3 hours, obtain carrier A, Main physical character sees Table 1.
B) preparation of sulfurized hydrogenation catalyst B
Take by weighing molybdenum oxide 28.48g, basic nickel carbonate 8.9g adds deionized water 60ml and mixes, and adds 85% phosphatase 24 ml, is heated to 75 ℃, and constant temperature 1 hour obtains deep green clear solution, adds the 30.2g ammonium metawolframate again and stirs, and promptly gets steeping fluid 1 after the dissolving.Measure steeping fluid 1 spray impregnated carrier A by water-intake rate 74ml/100g, 120 ℃ of dryings 3 hours dry sample, get with the ammonium sulfide of steeping fluid equivalent and phosphoric acid (85%) and stream and spray dry sample, (NH
4)
2S and H
3PO
4Mass ratio be 10: 1, promptly got catalyst B in 3 hours in 100 ℃ of dryings, Main physical character sees Table 1.
C) catalyzer start-up method and evaluation
Directly be warming up to 300 ℃ after the reactor that catalyzer is housed imports hydrogen, constant temperature 3 hours rises to temperature of reaction subsequently, introduces stock oil and carries out catalyzed 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 sulfurized hydrogenation catalyst C
Get steeping fluid 1 among the embodiment 1 and ammonium sulfide by water-intake rate 74ml/100g and flow sprayed carrier A, steeping fluid 1 is 1: 1 with the volume ratio of ammonium sulfide, promptly gets catalyzer C in 3 hours in 100 ℃ of dryings, and 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 sulfurized hydrogenation catalyst D
Get ammonium sulfide by water-intake rate 74ml/100g spray impregnated carrier, in 50 ℃ of dryings 6 hours dry sample, use the steeping fluid 1 spray impregnation drying sample among the embodiment 1 with ammonium sulfide equivalent, promptly got catalyzer D 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 hydrogen, constant temperature was introduced stock oil and is carried out catalyzed reaction after 3 hour.Operational condition is identical with embodiment 1.Evaluation result sees Table 2.
Comparative example 1
A) preparation of oxidation catalyst E
With the steeping fluid 1 of preparation among the embodiment 1, press water-intake rate 74ml/100g spray impregnated carrier A, 120 ℃ of dryings 3 hours dry sample, 500 ℃ of roastings 3 hours must catalyzer E, Main physical character sees Table 1.
B) start-up method of oxidation catalyst and evaluation
Oxidation catalyst is packed in the hydrogenator, after the reactor that catalyzer is housed imports hydrogen, directly be warming up to 120 ℃, advance vulcanized oil (being the mixture of boat coal and dithiocarbonic anhydride), rise to 350 ℃ subsequently and carry out prevulcanized, be 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
| Specific surface m 2/g | Mean pore size nm | Pore volume cm 3/g | Intensity N/cm | |
| Carrier A | 274.5 | 8.96 | 0.87 | 186 |
| Catalyst B | 196.1 | 6.84 | 0.62 | 174 |
| Catalyzer C | 184.7 | 6.61 | 0.64 | 182 |
| Catalyzer D | 200.4 | 7.12 | 0.62 | 170 |
| Catalyzer E | 203.9 | 7.06 | 0.68 | 165 |
The hydrogenation activity evaluation result of table 2 catalyzer
Claims (10)
1. the start-up method of a sulfurized hydrogenation catalyst comprises following content:
1) sulfurized hydrogenation catalyst is packed in the reactor;
2) feed the air that reaches in the hydrogen exchange reactor in the pipeline of reactor front and back, progressively be warming up to thermal treatment temp, system pressure can be any pressure that reactor can bear;
3) adjust pressure and temperature after the thermal treatment to reaction pressure and temperature of reaction, advance stock oil and begin to carry out hydrogenation reaction;
Described sulfurized hydrogenation catalyst adopts following method preparation:
1) chooses alumina supporter;
2) introduce the reactive metal of required kind and quantity with pickling process, before introducing reactive metal, introduce vulcanizing agent afterwards or simultaneously;
3) drying promptly gets sulfurized hydrogenation catalyst then.
2. in accordance with the method for claim 1, it is characterized in that: step 2 goes into operation) in thermal treatment temp be 200～400 ℃, the time is 1～10h; System pressure is a normal pressure, or any reactor pressure that can bear.
3. in accordance with the method for claim 1, it is characterized in that: among the sulfurized hydrogenation catalyst preparation method, the pore volume＞0.4ml/g of the alumina supporter of choosing, specific surface＞150m
2/ g.
4. in accordance with the method for claim 1, it is characterized in that: described vulcanizing agent is water-soluble sulphide salt, comprises in sodium sulphite, ammonium sulfide, hydrogen sulfide ammonium, thiocarbamide, dithiocar-bamate and the dithioglycol one or more.
5. in accordance with the method for claim 1, the consumption that it is characterized in that described vulcanizing agent is 1～5 times of the required sulfur content of active ingredient complete cure.
6. in accordance with the method for claim 1, the consumption that it is characterized in that described vulcanizing agent is 1～1.5 times of the required sulfur content of active ingredient complete cure.
7. in accordance with the method for claim 1, it is characterized in that in the described sulfurized hydrogenation catalyst preparation process, carry out drying treatment after introducing reactive metal and introducing the vulcanizing agent process, drying conditions is 20 ℃～200 ℃ dryings 1～10 hour down.
8. in accordance with the method for claim 1, the preparation method who it is characterized in that described sulfurized hydrogenation catalyst is:
(1) group VIII and IVB family metal inorganic salt are dissolved in acidity or basic solution, are made into the solution of desired concn;
(2) solution with step (1) preparation adopts saturated pickling process or excessive pickling process impregnation catalyst agent carrier, and following dry 1～10 hour at 20～200 ℃;
(3) adopt saturated pickling process or excessive pickling process impregnation steps (2) gained material with the vulcanizing agent aqueous solution;
(4) step (3) gained material was in 20～200 ℃ of dryings 1～10 hour.
9. in accordance with the method for claim 1, the preparation method who it is characterized in that described sulfurized hydrogenation catalyst is:
(1) adopt saturated pickling process or excessive pickling process impregnation catalyst agent carrier with the vulcanizing agent aqueous solution, and following dry 1～10 hour at 20～200 ℃;
(2) group VIII and IVB family metal inorganic salt are dissolved in acidity or basic solution, are made into the solution of desired concn;
(3) adopt the gains of saturated pickling process or excessive pickling process impregnation steps (1) with step (2) prepared solution;
(4) step (3) gained material is following dry 1～10 hour at 20～200 ℃.
10. in accordance with the method for claim 1, the preparation method who it is characterized in that described sulfurized hydrogenation catalyst is:
(1) group VIII and IVB family metal inorganic salt are dissolved in acidity or basic solution, are made into the solution of desired concn and pH value;
(2) adopt saturated pickling process or excessive pickling process to spray the impregnation catalyst agent carrier jointly with step (1) prepared solution and the vulcanizing agent aqueous solution, following dry 1～10 hour at 20～200 ℃ then.
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