CN101693214B - Ex-situ presulfurization method of hydrofining catalysts - Google Patents
Ex-situ presulfurization method of hydrofining catalysts Download PDFInfo
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- CN101693214B CN101693214B CN200910217726XA CN200910217726A CN101693214B CN 101693214 B CN101693214 B CN 101693214B CN 200910217726X A CN200910217726X A CN 200910217726XA CN 200910217726 A CN200910217726 A CN 200910217726A CN 101693214 B CN101693214 B CN 101693214B
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Abstract
The invention relates to an ex-situ presulfurization method of hydrofining catalysts. The method includes: placing dixanthogen into a beaker; adding industrial white oil into the beaker; heating the beaker to lead the dixanthogen and the white oil to be mutually dissolved to form white oil dixanthogen liquor; adding the presulfurization hydrofining catalysts into the beaker according to a certain proportion and mixing evenly; placing the presulfurization hydrofining catalysts absorbing fully the white oil dixanthogen liquor into a pressure kettle after finishing immersion; and finishing the ex-situ presulfurization of the hydrofining catalysts by heating the liquor for a certain period under certain temperature and pressure and then cooling the liquor to room temperature. The method breaks through a conventional sulfurization method of the hydrofining catalysts, reduces carbon deposit quantity of the hydrofining catalysts, improves sulfur absorption rate, apparently improves activity and stability of the hydrofining catalysts, enables the hydrofining catalysts to stably exist in air and be convenient for transportation and storage, greatly decreases cost of industrial hydrogenation and has simple operation, easy implementation and even presulfurization. Compared with the conventional presulfurization method, the method can remarkably lower cost of sulfurization.
Description
Technical field:
The present invention relates to petrochemical industry petroleum refining industry technology, especially the sulfuration pretreating process of hydrogenation catalyst in the catalytic hydrogenation technology.
Background technology:
Along with developing rapidly and technological progress of petroleum refining industry, the catalytic hydrogenation technology is used widely in petroleum and petrochemical industry enterprise.For overcoming insufficient and catalyst long deficiency on-stream time of the sulfuration of presulfurization in the hydrogenating catalyst, develop the outer pre-curing technology of hydrogenating catalyst.This technology can make hydrogenation catalyst obtain efficient vulcanization, compares with presulfurization in the device, and its technical advantage is: the one, and the outer pre-curing technology of device can make the utilization rate of activity of hydrocatalyst metal component improve, and catalyst vulcanization gets more abundant; The 2nd, the outer pre-curing technology of device can be saved the on-stream time of catalyst, further simplifies the program that goes into operation of catalyst; The 3rd, poisonous sulfide can be avoided using in the scene of going into operation of the catalyst of the outer presulfurization of device; The 4th, when being used for industrial catalyst and casting aside, more can embody the outer pre-sulfide catalyst of the device easy characteristics that go into operation.Adopt the sulfuration that can directly heat up when going into operation of the outer presulfurization hydrogenation catalyst of device, during situation that the operating pressure that particularly runs into reactor is lower, logistics is uneven, device pre-sulfide catalyst outward still can reach cure efficiency preferably.
The method for pre-sulphuration that CN1262305 discloses " a kind of method for pre-sulphuration of hydrogenation catalyst " hydrogenation catalyst comprises that component, elementary sulfur and the auxiliary agent that will contain alkene mix, heat described mixtures more than 0.5 hour at 100～220 ℃, the molal quantity of elementary sulfur is no less than the molal quantity of olefinic double bonds, auxiliary dosage is 10～80 heavy % of elementary sulfur consumption, and described auxiliary agent is selected from vulcanization of rubber organic additive commonly used; The product that obtains dipping is introduced the catalyst of elementary sulfur, and under inert atmosphere in 100～300 ℃ of heatable catalysts more than 1 hour; Wherein, the volumetric usage of described product is at least 60% of catalyst pore volume.The last sulfur content of this invention is often held the sulfur content deficiency owing to be subjected to the double-stranded limited in number of alkene to high metals content catalysts.
It is as follows that CN1602999 discloses " the outer pretreated method of a kind of hydrogenating catalyst " this method step: the outer gas phase presulfurization of the device of the hydrogenation catalyst of (1) oxidation state joins the solid catalyst of oxidation state in the vulcanization reaction device, inert gas purge vulcanization reaction device, curing system is warmed up to 80～300 ℃ simultaneously, under 0.1～10MPa pressure, introduce sulfuration gas, 150～600 ℃ of vulcanization reactions 0.5～50 hour; (2) gaseous passivation of sulphided state catalyst is handled the sulphided state catalyst after step (1) sulfuration, through inert gas purge, catalyst temperature is reduced to 30～200 ℃, under 30～200 ℃, introduce and contain the oxygen passivating gas, make the oxygen concentration of volume percent 0.1～21% Passivation Treatment 0.5～10 hour, concentration of oxygen is along with the passivation reaction time-program(me) increases, and the long-pending percent concentration of carrier of oxygen is brought up to 18-24%, Passivation Treatment 0.5～10 hour the most at last.This invents described method instability, needs protection and can realize.
Summary of the invention:
Purpose of the present invention just is to provide a kind of ex-situ presulfiding method of hyrorefining catalysts at above-mentioned the deficiencies in the prior art.
The objective of the invention is by following technology side by realizing:
Ex-situ presulfiding method of hyrorefining catalysts comprises following order and step:
A, get double xanthate 20% and put into beaker, add 80% technical white oil, be heated to the double xanthate fusing, and dissolve each other with white oil and to form white oil double xanthate solution, the mass ratio of white oil and double xanthate is 1: 4;
B, add the presulfurization Hydrobon catalyst in white oil double xanthate solution, and mix, the mass ratio of white oil double xanthate solution and Hydrobon catalyst is 1: 5;
After c, dipping finish, the Hydrobon catalyst of inhaling full white oil double xanthate solution is packed in the autoclave pressure, 200 ℃ of-250 ℃ of temperature, heating 1-2 hour down of 0.2MPa pressure is cooled to room temperature, promptly finishes the outer presulfurization of Hydrobon catalyst device.
Purpose of the present invention can also be pressed by following technology side and be realized:
Double xanthate described in the step a is any in two ethoxy-dithioformic acid ester disulphide, two isopropyl xanthan acid esters disulphide, two butyl xanthic acid ester disulphide or the two amyl group xanthate disulphide.
Preferred No. 7 technical white oils of technical white oil described in the step a.
Beneficial effect: the present invention has broken through the method for traditional catalyst vulcanization, sulfuration has evenly reduced the coke content of catalyst, has improved sulfurization rate, activity of such catalysts and stability are significantly improved, can stable in the airly exist, be convenient to transportation and storage, greatly reduce industrial hydrogenation cost, simple to operate, easy to implement, the vulcanization process comparison with traditional can significantly reduce the sulfuration cost.
The specific embodiment:
In implementing, be described in further detail:
Ex-situ presulfiding method of hyrorefining catalysts comprises following order and step:
Ex-situ presulfiding method of hyrorefining catalysts comprises following order and step:
A, get double xanthate 20% and put into beaker, add 80% technical white oil, be heated to the double xanthate fusing, and dissolve each other with white oil and to form white oil double xanthate solution, the mass ratio of white oil and double xanthate is 1: 4;
B, add the presulfurization Hydrobon catalyst in white oil double xanthate solution, and mix, the mass ratio of white oil double xanthate solution and Hydrobon catalyst is 1: 5;
After c, dipping finish, the Hydrobon catalyst of inhaling full white oil double xanthate solution is packed in the autoclave pressure, 200 ℃ of-250 ℃ of temperature, heating 1-2 hour down of 0.2MPa pressure is cooled to room temperature, promptly finishes the outer presulfurization of Hydrobon catalyst device.
Purpose of the present invention can also be pressed by following technology side and be realized:
Double xanthate described in the step a is any in two ethoxy-dithioformic acid ester disulphide, two isopropyl xanthan acid esters disulphide, two butyl xanthic acid ester disulphide or the two amyl group xanthate disulphide.
Preferred No. 7 technical white oils of technical white oil described in the step a.
Embodiment 1
A, get double xanthate 20g and put into beaker, add the 80g7 technical white oil, be heated to the double xanthate fusing, and dissolve each other with white oil and to form white oil double xanthate solution;
B, in white oil double xanthate solution, add presulfurization Hydrobon catalyst 500g, and mix;
After c, dipping finish, the Hydrobon catalyst of inhaling full white oil double xanthate solution is packed in the autoclave pressure, 220 ℃ of temperature, the heating 1.5 hours down of 0.2MPa pressure is cooled to room temperature, promptly finishes the outer presulfurization of Hydrobon catalyst device.
Embodiment 2
A, get double xanthate 10g and put into beaker, add the 40g technical white oil, be heated to the double xanthate fusing, and dissolve each other with white oil and to form white oil double xanthate solution;
B, in white oil double xanthate solution, add presulfurization Hydrobon catalyst 250g, and mix;
After c, dipping finish, the Hydrobon catalyst of inhaling full white oil double xanthate solution is packed in the autoclave pressure, 200 ℃ of temperature, the heating 1 hour down of 0.2MPa pressure is cooled to room temperature, promptly finishes the outer presulfurization of Hydrobon catalyst device.
Embodiment 3
A, get double xanthate 40g and put into beaker, add the 160g technical white oil, be heated to the double xanthate fusing, and dissolve each other with white oil and to form white oil double xanthate solution;
B, in white oil double xanthate solution, add presulfurization Hydrobon catalyst 1000g, and mix;
After c, dipping finish, the Hydrobon catalyst of inhaling full white oil double xanthate solution is packed in the autoclave pressure, 240 ℃ of temperature, the heating 2 hours down of 0.2MPa pressure is cooled to room temperature, promptly finishes the outer presulfurization of Hydrobon catalyst device.
Embodiment 4
A, get double xanthate 50g and put into beaker, add the 200g technical white oil, be heated to the double xanthate fusing, and dissolve each other with white oil and to form white oil double xanthate solution;
B, in white oil double xanthate solution, add presulfurization Hydrobon catalyst 1250g, and mix;
After c, dipping finish, the Hydrobon catalyst of inhaling full white oil double xanthate solution is packed in the autoclave pressure, 250 ℃ of temperature, the heating 2 hours down of 0.2MPa pressure is cooled to room temperature, promptly finishes the outer presulfurization of Hydrobon catalyst device.
Claims (3)
1. an ex-situ presulfiding method of hyrorefining catalysts is characterized in that, comprises following order and step:
A, get double xanthate 20% and put into beaker, add 80% technical white oil, be heated to the double xanthate fusing, and dissolve each other with white oil and to form white oil double xanthate solution, the mass ratio of white oil and double xanthate is 1: 4;
B, add the presulfurization Hydrobon catalyst in white oil double xanthate solution, and mix, the mass ratio of white oil double xanthate solution and Hydrobon catalyst is 1: 5;
After c, dipping finish, the Hydrobon catalyst of inhaling full white oil double xanthate solution is packed in the autoclave pressure, 200 ℃ of-250 ℃ of temperature, heating 1-2 hour down of 0.2MPa pressure is cooled to room temperature, promptly finishes the outer presulfurization of Hydrobon catalyst device.
2. according to the described a kind of ex-situ presulfiding method of hyrorefining catalysts of claim 1, it is characterized in that the double xanthate described in the step a is any in two ethoxy-dithioformic acid ester disulphide, two isopropyl xanthan acid esters disulphide, two butyl xanthic acid ester disulphide or the two amyl group xanthate disulphide.
3. according to the described a kind of ex-situ presulfiding method of hyrorefining catalysts of claim 1, it is characterized in that preferred No. 7 technical white oils of the technical white oil described in the step a.
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Effective date of registration: 20161026 Address after: 116000 A, building -A7-1, colorful city, Dalian economic and Technological Development Zone, Liaoning, China Patentee after: Dalian Engineering Construction Co., Ltd. Address before: Our high tech Development Zone in Jilin province Changchun 130012 Street No. 286 Patentee before: Changchun Huigong Purifying Industry Co., Ltd. |
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