CN109926100A - A kind of start-up method of sulfurized hydrogenation catalyst - Google Patents
A kind of start-up method of sulfurized hydrogenation catalyst Download PDFInfo
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Abstract
The invention discloses a kind of start-up methods of sulfurized hydrogenation catalyst, the start-up method includes following content: sulfurized hydrogenation catalyst composition is fitted into reactor, it is airtight to carry out nitrogen, hydrogen is gradually introducing after the airtight qualification of nitrogen, it is airtight to carry out hydrogen low pressure, it is airtight to carry out high pressure for increasing temperature and pressure after the closely sealed lattice of low pressure gas；After the closely sealed lattice of high pressure gas, adjustment pressure to reaction pressure finally adjusts temperature to reaction temperature, starts to carry out hydrogenation reaction into feedstock oil to completion is vulcanized.The start-up method not only can guarantee the vulcanized quality of catalyst, but also can solve the airtight problem of device, and no pollution to the environment, economic and environment-friendly.
Description
Technical field
The present invention relates to a kind of start-up method of catalyst, especially a kind of start-up method of hydrogenation catalyst.
Background technique
Crude oil in poor quality tendency is increasingly apparent in recent years, and demand of the various countries to clean fuel increasingly increases, and adds hydrogen work
Skill is closed as one of production most effective means of clean fuel with the technology that its efficient hydrogenation catalyst becomes hydrogenation technique
Key.Conventional activity of hydrocatalyst metal is oxidation state, and the substance for really playing active function in actual use is sulphided state,
So need to be vulcanized in reactor before use.
Conventional hydrogenation catalyst is oxidation state, and the substance for really playing active function in actual use is sulphided state, institute
Need to be vulcanized in reactor before use.A kind of typical in-situ presulfurization side is described in patent CN1171430A
Method, wherein vulcanizing agent selects carbon disulfide or dimethyl disulfide etc., and the volume ratio of vulcanizing agent gas and catalyst is generally 300
~600, vulcanization carries out at atmospheric pressure or elevated pressure, and general heating and constant temperature program are that vulcanization 2~6 is small at 200~240 DEG C
When, then vulcanize 8~12 hours at 320~360 DEG C.Since in-situ presulfurization is carried out in refinery, special equipment is needed, this is not only
Production cost is increased, and vulcanizes and is easy to pollute human and environment, therefore scientific research personnel actively seeks to solve both at home and abroad
Method, ex situ presulfiding come into being.
Ex situ presulfiding refers to that catalyst in conjunction with vulcanizing agent, is reloaded into reactor before being packed into reactor.When going into operation,
It needs to be passed through H2, as the temperature rises, vulcanizing agent, which decomposes, generates hydrogen sulfide, so that hydrogenation active metals be made to be converted into vulcanization
Object.CN1362493A discloses a kind of vulcanization process of catalyst for hydroprocessing of heavy oil, its main feature is that by solid sulfide with
Catalyst mixing vulcanizes the means combined using low-temperature dry vulcanization and high temperature wet, so that sulfide type catalyst be made.With
Vulcanization is compared in device, and ex situ presulfiding technology is short with on-stream time, Star-up is simple, refinery equipment small investment, endangers to people
The advantages that small and environmental pollution of evil is small.CN200910204284.5 discloses a kind of start-up method of Residue Hydrotreating Technology,
By the requirement of Residue Hydrotreating Technology, ex situ presulfiding is carried out to selected catalyst, catalyst is packed into reactor, heating, activation
Afterwards, switching residual oil raw material carries out hydrotreating.The partial catalyst that this method only needs Residue Hydrotreating Technology carries out pre- outside device
Vulcanizing treatment saves production cost outside retainer while pre-vulcanization process advantage, reduces catalyst attrition.This two
The presulfurization raw material of a patent is solid sulfur, and decomposition temperature is 100 DEG C or so under hydrogen, due to the reactor of hydrogenation plant
The considerations of limitation of material and production security etc., the high pressure of device is airtight to be reached in the minimum temperature of whole device
92 DEG C, the inlet temperature of such reactor is at least up to 150 DEG C or more and carries out, and it is anti-that vulcanization is had begun before device high temperature is airtight
It answers.Hydrogen sulfide enters in recycle hydrogen before airtight, once airtight unqualified emptying, then cause vulcanizing agent insufficient and then influence to urge
The vulcanization effect of agent.Therefore the airtight problem of device has become ex situ presulfiding technical application at present and promotes difficulty urgently to be resolved
Topic.
Summary of the invention
In view of the deficiencies of the prior art, it the present invention provides a kind of start-up method of sulfurized hydrogenation catalyst, went into operation
For carbon monoxide-olefin polymeric used in journey in vulcanization, organic sulfur compound, organic compound and hydrazine hydrate form intermediate under low temperature
Fixed sulfide, goes on smoothly the airtight of device, organic compound and organic sulfur compound after temperature rises to certain altitude
It decomposes, organic sulfur compound and hydrogen and metal reaction carry out the vulcanization of catalyst.The catalyst is not necessarily to outer add when going into operation and vulcanizing
Vulcanizing agent, not only can guarantee the vulcanized quality of catalyst, but also can solve the airtight problem of device.
For the deficiencies in the prior art, the present invention provides a kind of start-up method of sulfurized hydrogenation catalyst,
The start-up method includes following content:
(1) sulfurized hydrogenation catalyst composition is fitted into reactor, it is airtight carries out nitrogen；
(2) it is gradually introducing hydrogen after the airtight qualification of nitrogen, progress hydrogen low pressure is airtight, heats up after the closely sealed lattice of low pressure gas, works as reaction
It is airtight that device inlet temperature to boosting after 130~180 DEG C carries out high pressure；
(3) after the closely sealed lattice of high pressure gas, adjustment pressure to reaction pressure then proceedes to be warming up to 200~250 DEG C, vulcanizes 3~12h
After be continuously heating to 270~320 DEG C, vulcanization 3~for 24 hours until vulcanization is completed；
(4) adjustment temperature starts to carry out hydrogenation reaction into feedstock oil to reaction temperature；
Wherein the sulfurized hydrogenation catalyst composition includes:
(1) oxidation state hydrogenation catalyst；
(2) organic sulfur compound, the organic sulfur compound dosage be hydrogenation catalyst metal component theory need sulfur content 85%~
150%, preferably 95%~120%；
(3) organic compound, the organic compound dosage are the 2%~50% of catalyst weight, preferably 5%~30%.
(4) hydrazine hydrate, the dosage of the hydrazine hydrate are the 20% ~ 120% of organic sulfur compound dosage, preferably 30 ~ 80%.
In start-up method of the present invention, pressure when low pressure described in step (2) is airtight is 1.0~3.0MPa, and high pressure is airtight
When pressure be the 120%~200% of reaction pressure, be subject to the operating pressure of specific device.In start-up method of the present invention, to protect
The safety of hydrogenation plant is demonstrate,proved, airtight pressure and temperature needs strictly to be operated in accordance with the requirement of pressure vessel, specific to grasp
It is well known to those skilled in the art as method.
In start-up method of the present invention, hydrogenation conditions such as reaction pressure, temperature, hydrogen-oil ratio and air speed etc. in step (4)
It is determined by those skilled in the art according to the property of the feedstock oil of reaction, purpose product requirement and catalyst performance.General reactions
Pressure is 1.0~20.0MPa, 150~450 DEG C of temperature, hydrogen-oil ratio 200~2000,1.0~10.0h of air speed-1.The raw material
Oil can be the various raw materials and its mixture that can add hydrogen.
In start-up method of the present invention, after high pressure gas closely sealed lattice, dry pre-sulfiding, both sulfidation not oil inlets can be used,
Also wet process vulcanization can be used, wet process vulcanization introduces the oil that goes into operation after airtight, and the oil that goes into operation is direct steaming gasoline, virgin kerosene and
One kind of straight-run diesel oil.
In above-mentioned start-up method, it generally can be sulfur-bearing that the organic sulfur compound, which is vulcanizing agent commonly used in the art,
The one or more of organic matter.Organic sulfur compound can for mercaptan, carbon disulfide, dimethyl disulfide (DMDS), dimethyl sulfide,
One or more of thioether, polysulfide, it is R-S that wherein polysulfide, which is selected from general formula,nOne kind of the organic polysulfide of-R '
Or it is a variety of, the value of n is 2-10, R and R ' may be the same or different, can be saturation or unsaturation, linear chain or branched chain,
The carbon atom number of naphthenic base or aromatic radical, R and R ' can be 1-10.
In above-mentioned start-up method, the organic compound is tetra methylol phosphonium salt and its homologue, is specifically as follows four
One or more of methylol phosphorus chloride and its homologue, tetrakis hydroxymetyl phosphonium sulfuric and its homologue, substituted hydro carbons can be with
It is identical, it can also be different, can be saturation or unsaturation, linear chain or branched chain, naphthenic base or aromatic radical, the carbon atom number of hydro carbons can
Think 1~10.It is specifically as follows four ethoxy phosphorus chloride, tetrahydroxy aniline methyl chloride phosphorus, tetrahydroxy benzene methyl chloride phosphorus, four
Hydroxypropyl phosphorus chloride, tetrahydroxy vinylimidazolium chloride phosphorus, four hydroxyethyl methyl sulfuric acid phosphorus, tetrahydroxy aniline methylsulfuric acid phosphorus, four
Hydroxyphenylmethyl sulfuric acid phosphorus, tetrahydroxypropyl sulfuric acid phosphorus, one or more of tetrahydroxy vinylsulfuric acid phosphorus.
In above-mentioned start-up method, the hydrogenation catalyst is at Hydrobon catalyst, hydrocracking catalyst plus hydrogen
Manage any one of catalyst.Generally using refractory inorganic oxides as carrier, such as aluminium oxide, silica, amorphous silicon aluminium, oxidation
Titanium, the composite oxides of molecular sieve and each several elements or mixing carrier of oxygen etc., active metal component is generally W, Mo, Ni
One or more of with Co, while auxiliary agent can be contained.Catalyst carrier for hydrgenating, active metal component and auxiliary agent selection and
Dosage can specifically be determined according to this field general knowledge according to the needs of application, for hydrocarbons hydrogenation catalyst, with oxygen
The hydrogenation metal component content of compound meter is generally the 1% ~ 90% of catalyst weight, and usually 3% ~ 50%.Hydrogenation catalyst is theoretical
Sulfur content is needed to be converted into sulfide (Co for institute's metallic components on catalyst9S8、MoS2、Ni3S2、WS2) when need the amount of sulphur.
In above-mentioned start-up method, the preparation method of the sulfide type catalyst composition includes the following steps: have described
Machine compound, organic sulfur compound and hydrazine hydrate are introduced on catalyst simultaneously, or substep is introduced on catalyst, organic introducing
Include at least one Low Temperature Heat Treatment step and do not include calcination steps during compound, organic sulfur compound and hydrazine hydrate.
Following several modes can be specifically used, (1) introduces organic sulfur compound, hydrazine hydrate and organic compound respectively, introduces every kind of group
Low Temperature Heat Treatment is carried out after point, the sequencing for introducing three kinds of substances can be arbitrary；(2) by organic sulfur compound, hydration
Hydrazine and organic compound are made into homogeneous solution, Low Temperature Heat Treatment after impregnation catalyst agent；(3) organic sulfur compound and hydration are first introduced
Hydrazine, Low Temperature Heat Treatment are re-introduced into organic compound, Low Temperature Heat Treatment.(4) organic compound, Low Temperature Heat Treatment are first introduced, then is drawn
Enter organic sulfur compound and hydrazine hydrate, Low Temperature Heat Treatment.
In the preparation method of above-mentioned hydrotreatment catalyst composition, the temperature of the Low Temperature Heat Treatment is 20~200 DEG C,
Preferably 60~160 DEG C, the time be 1~for 24 hours, preferably 3~12h.
In the preparation method of above-mentioned hydrotreatment catalyst composition, the Low Temperature Heat Treatment can be in air, nitrogen or lazy
It is carried out under property gas atmosphere.
Compared with prior art, start-up method of the present invention has the advantages that
1, present invention employs a kind of completely new start-up method, ex situ presulfiding catalyst device when going into operation ideally is solved
The problem of high temperature is airtight and vulcanizing agent low temperature overflows, during catalyst vulcanization, organic compound and organic sulfide when low temperature
Object forms intermediate, and fixed sulfide inhibits the spilling of vulcanizing agent, makes the high temperature of device is airtight to go on smoothly, when temperature rises
The intermediate that organic compound and sulfide are formed after to certain altitude decomposes, and organic sulfur compound and hydrogen and metal reaction carry out
The vulcanization of catalyst, not only can guarantee the vulcanized quality of catalyst, but also can solve the airtight problem of device.
2, the organic compound in inventive catalyst composition under the action of hydrazine hydrate can be with organic sulfur compound
Intermediate is formed in the preparation process of ex situ presulfiding catalyst, the intermediate uniform load of generation is on the surface and hole of catalyst
In road, keep the vulcanization of catalyst uniformly and thorough, is conducive to the hydrogenation activity for improving catalyst.And the organic compound and
A variety of organic sulfur compounds match, and can also make the exothermic peak disperse of vulcanization reaction, avoid bed temperature runaway.
Specific embodiment
The technical characterstic that the invention is further illustrated by the following examples, but these embodiments cannot limit the present invention.
Embodiment 1
(1) preparation of hydrogenation catalyst A
Industrial oxidized catalyst 100g is taken, sprays catalyst after taking DMDS18g to mix with hydrazine hydrate 10ml, by sample
It is put into progress first time Low Temperature Heat Treatment, first time Low Temperature Heat Treatment condition are as follows: with the rate liter of 3 DEG C/min in air dry oven
Temperature is to 80 DEG C, constant temperature 3 hours.Take the sample of tetrakis hydroxymetyl phosphonium sulfuric aqueous solution (75wt%) 50g spray first time Low Temperature Heat Treatment
Sample is put into air dry oven after spray and carries out second of Low Temperature Heat Treatment by product, second of Low Temperature Heat Treatment condition and the
It is primary identical to get hydrotreating catalyst A.
(2) catalyst start-up method and evaluation
Sulfurized hydrogenation catalyst is fitted into reactor, it is airtight to carry out nitrogen；It is gradually introducing hydrogen after the airtight qualification of nitrogen, into
Row hydrogen low pressure is airtight, and airtight pressure is 2.0MPa, heating furnace firing up after airtight qualification, until reactor inlet temperature 150
DEG C start boosting airtight, the airtight pressure 10MPa that carries out high pressure, is down to reaction pressure 7.2MPa after the closely sealed lattice of high pressure gas, introducing is opened
Work oil straight-run diesel oil, constant temperature are continuously heating to 200 DEG C after 4 hours, vulcanized within constant temperature 8 hours, be continuously heating to 280 later
DEG C, constant temperature vulcanization in 8 hours is completed.Catalytic diesel oil is changed to, is continuously heating to 350 DEG C of reaction temperature, sampling analysis after constant temperature 8h.Sulphur
Analysis is sampled to tail gas during change, the content of hydrogen sulfide and sulfide is shown in Tables 1 and 2.The reaction condition of catalytic diesel oil
Are as follows: pressure 7.2MPa, air speed 1.5,350 DEG C of temperature, hydrogen-oil ratio 1000.Its density of catalytic diesel oil is 0.890g/cm3, sulfur content
For 10453 μ g/g, nitrogen content is 852 μ g/g, and evaluation result is shown in Table 3.
Embodiment 2
(1) preparation of hydrogenation catalyst B
Industrial oxidized catalyst 100g is taken, DMDS18g and hydrazine hydrate 10ml mixed liquor, tetrakis hydroxymetyl phosphonium sulfuric water are taken
Solution (solution concentration 75wt%) 50g, by the two cocurrent spray catalyst after, sample is put into air dry oven carry out it is low
Warm processing, Low Temperature Heat Treatment condition are as follows: be warming up to 80 DEG C, constant temperature 3 hours with the rate of 3 DEG C/min.It is urged up to hydrotreating
Agent B.
(2) catalyst start-up method and evaluation
Catalyst start-up method and evaluation are identical as (2) the step of embodiment 1, and the content of hydrogen sulfide and sulfide is shown in Table 1 and table
2.Evaluation result is shown in Table 3.
Embodiment 3
(1) preparation of hydrogenation catalyst C
Industrial oxidized catalyst 100g is taken, takes carbon disulfide 13g, hydrazine hydrate 12ml to mix, adds four ethoxys
Sulfuric acid phosphorus aqueous solution 65ml stirs 20min containing four ethylene hydroxy sulfuric acid phosphorus 36g, forms uniform solution and sprays catalyst, sample is put
Enter and carry out Low Temperature Heat Treatment, treatment conditions in air dry oven are as follows: is warming up to 80 DEG C, constant temperature 3 hours with the rate of 3 DEG C/min.
Up to hydrotreating catalyst C.
(2) catalyst start-up method and evaluation
Sulfurized hydrogenation catalyst is fitted into reactor, it is airtight to carry out nitrogen；It is gradually introducing hydrogen after the airtight qualification of nitrogen, into
Row hydrogen low pressure is airtight, and airtight pressure is 2.0MPa, heating furnace firing up after airtight qualification, until reactor inlet temperature 150
DEG C start boosting airtight, the airtight pressure 10MPa that carries out high pressure, reaction pressure 7.2MPa is down to after the closely sealed lattice of high pressure gas, after of continuing rising
Temperature is vulcanized for constant temperature 8 hours to 200 DEG C, is continuously heating to 280 DEG C later, constant temperature vulcanization in 8 hours is completed.Introduce catalysis bavin
Oil is continuously heating to 350 DEG C of reaction temperature, sampling analysis after constant temperature 8h.Analysis is sampled to tail gas in sulfidation, is vulcanized
The content of hydrogen and sulfide is shown in Tables 1 and 2.Feedstock oil and process conditions are identical as (2) the step of embodiment 1.Evaluation result is shown in
Table 3.
Embodiment 4
(1) preparation of hydrogenation catalyst D
Take industrial oxidized catalyst 100g, after taking DMDS9g and dimethyl sulfoxide 13g to mix again with 10ml hydrazine hydrate
Mixing sprays catalyst, and sample is put into progress first time Low Temperature Heat Treatment, first time Low Temperature Heat Treatment item in air dry oven
Part are as follows: be warming up to 100 DEG C, constant temperature 3 hours with the rate of 3 DEG C/min.Tetramethylol chloride 17g is taken, is sprayed after being diluted with 50g water
The sample of first time Low Temperature Heat Treatment is drenched, sample is put into air dry oven after spray and carries out second of Low Temperature Heat Treatment, the
Secondary Low Temperature Heat Treatment condition is to be warming up to 120 DEG C, constant temperature 3 hours with the rate of 3 DEG C/min.Up to hydrotreating catalyst D.
(2) catalyst start-up method and evaluation
Catalyst start-up method and evaluation are identical as (2) the step of embodiment 1, and the content of hydrogen sulfide and sulfide is shown in Table 1 and table
2.Evaluation result is shown in Table 3.
Embodiment 5
(1) preparation of hydrogenation catalyst E
Industrial oxidized catalyst 100g is taken, sprays catalyst after taking DMDS18g to mix with hydrazine hydrate 10ml, by sample
It is put into progress first time Low Temperature Heat Treatment, first time Low Temperature Heat Treatment condition are as follows: with the rate liter of 3 DEG C/min in air dry oven
Temperature is to 80 DEG C, constant temperature 3 hours.Four hydroxy toluene amido phosphorus chloride 36g are taken, with spray first time Low Temperature Heat Treatment after the dilution of 50g water
Sample, sample is put into air dry oven after spray and carries out second of Low Temperature Heat Treatment, second of Low Temperature Heat Treatment condition
It is identical as first time to get hydrotreating catalyst E.
(2) catalyst start-up method and evaluation
Catalyst start-up method and evaluation are identical as (2) the step of embodiment 1, and the content of hydrogen sulfide and sulfide is shown in Table 1 and table
2, evaluation result is shown in Table 3.
Comparative example 1
(1) preparation of hydrogenation catalyst F
Take industrial oxidized catalyst 100g, take DMDS18g spray after, sample is put into air dry oven carry out it is low
Warm processing, Low Temperature Heat Treatment condition are as follows: be warming up to 120 DEG C, constant temperature 3 hours with the rate of 3 DEG C/min.It is urged up to hydrotreating
Agent F.
(2) catalyst start-up method and evaluation
Catalyst start-up method and evaluation are identical as (2) the step of embodiment 1, and the content of hydrogen sulfide and sulfide is shown in Table 1 and table
2, evaluation result is shown in Table 3.
Comparative example 2
(1) preparation of hydrogenation catalyst G
Take industrial oxidized catalyst 100g, take carbon disulfide 13g spray after, by sample be put into air dry oven into
Row Low Temperature Heat Treatment, first time Low Temperature Heat Treatment condition are as follows: be warming up to 80 DEG C, constant temperature 3 hours with the rate of 3 DEG C/min.To obtain the final product
Hydrotreating catalyst G.
(2) catalyst start-up method and evaluation
Catalyst start-up method and evaluation are identical as (2) the step of embodiment 1, and the content of hydrogen sulfide and sulfide is shown in Table 1 and table
2, evaluation result is shown in Table 3.
Comparative example 3
(1) preparation of hydrogenation catalyst H
It is same as Example 1, it is only addition hydrazine hydrate.Obtain catalyst H.
(2) catalyst start-up method and evaluation
Catalyst start-up method and evaluation are identical as (2) the step of embodiment 1, and the content of hydrogen sulfide and sulfide is shown in Table 1 and table
2, evaluation result is shown in Table 3.
Comparative example 4
(1) preparation of hydrogenation catalyst J
Industrial oxidized catalyst 100g is taken, carbon disulfide 13g is taken to spray catalyst, ageing took four hydroxyls after 2 hours again
Ethyl sulfuric acid phosphorus aqueous solution 65ml(contain four ethylene hydroxy sulfuric acid phosphorus 36g) spray catalyst, by sample be put into air dry oven into
Row Low Temperature Heat Treatment, treatment conditions are as follows: be warming up to 80 DEG C, constant temperature 3 hours with the rate of 3 DEG C/min.Up to hydrorefining catalyst
Agent J.
(2) catalyst start-up method and evaluation
Catalyst start-up method and evaluation are identical as (2) the step of embodiment 1, and the content of hydrogen sulfide and sulfide is shown in Table 1 and table
2, evaluation result is shown in Table 3.
The activity rating of 1 oxidized form hydrogenation catalyst of test case
The oxidized catalyst for taking experiment used carries out activity stability evaluation, airtight process and (2) phase the step of embodiment 1
Together, it to be down to reaction pressure 7.2MPa after airtight qualification, started into sulfurized oil, sulfurized oil is the mixture of boat coal and carbon disulfide,
Its density is 0.798g/cm3, sulfur content is 20000 μ g/g, and nitrogen content is 1.0 μ g/g, and boiling range is 161~276 DEG C.Constant temperature 4 is small
When, then 230 DEG C are risen to the heating rate of 20 DEG C/h, constant temperature 8 hours, then be warming up to 320 DEG C of constant temperature and complete vulcanization after 8 hours.
Then swap-in catalytic diesel oil is warming up to sampling analysis after 350 DEG C, then constant temperature 8 hours.Tail gas is sampled point in sulfidation
The content of analysis, hydrogen sulfide and sulfide is shown in Tables 1 and 2.Feedstock oil and process conditions are identical as (2) the step of embodiment 1.Evaluation
It the results are shown in Table 3.
Sulfide analysis result (sulfide except vulcanisation hydrogen) in 1 tail gas of table
Hydrogen sulfide analyzes result in 2 tail gas of table
The evaluation result of 3 catalyst of table
Organic sulfur compound is directly loaded on catalyst it can be seen from table 1, table 2, at low temperature i.e. 120 DEG C -130 DEG C when sulphur
Compound is overflowed out of catalyst duct, and the high pressure of device is airtight generally at 150 DEG C, if airtight unqualified, emptying will loss
Vulcanizing agent makes subsequent metal vulcanization not exclusively, influences the activity of catalyst.And the organic compound in catalyst of the invention
Adsorb complexing under the action of hydrazine hydrate with organic sulfur compound, uniform load is in the surface and duct of catalyst, in catalyst
When vulcanization under low temperature < complex compound that is formed with organic sulfur compound of 180 DEG C of organic compounds do not decompose, fixed sulfide hinders it
With reacting for hydrogen, make the high temperature of device is airtight to go on smoothly, organic compound and sulfide solution after temperature rises to 180 DEG C
Network, sulfide and hydrogen and metal reaction carry out the vulcanization of catalyst, not only can guarantee the vulcanized quality of catalyst, but also can solve dress
The airtight problem set.As shown in Table 3, the hydrogenation activity of catalyst is high, and the preparation process of catalyst is simple, good economy performance.Catalysis
Agent is sulfide type catalyst, and start-up process is simple, is greatly decreased the time required to going into operation.
Claims (16)
1. a kind of start-up method of sulfurized hydrogenation catalyst, the start-up method includes following content:
(1) sulfurized hydrogenation catalyst composition is fitted into reactor, it is airtight carries out nitrogen；
(2) it is gradually introducing hydrogen after the airtight qualification of nitrogen, progress hydrogen low pressure is airtight, heats up after the closely sealed lattice of low pressure gas, works as reaction
It is airtight that device inlet temperature to boosting after 130~180 DEG C carries out high pressure；
(3) after the closely sealed lattice of high pressure gas, adjustment pressure to reaction pressure then proceedes to be warming up to 200~250 DEG C, vulcanizes 3~12h
After be continuously heating to 270~320 DEG C, vulcanization 3~for 24 hours until vulcanization is completed；
(4) adjustment temperature starts to carry out hydrogenation reaction into feedstock oil to reaction temperature；
Wherein the sulfurized hydrogenation catalyst composition includes: oxidation state hydrogenation catalyst, organic sulfur compound, organic compound
And hydrazine hydrate.
2. the start-up method of sulfurized hydrogenation catalyst described in accordance with the claim 1, wherein low pressure gas described in step (2)
Pressure when close is 1.0~3.0MPa, and pressure when high pressure is airtight is the 120%~200% of reaction pressure, with the behaviour of specific device
Make subject to pressure.
3. the start-up method of sulfurized hydrogenation catalyst described in accordance with the claim 1, wherein after high pressure gas closely sealed lattice, adopt
Vulcanized with dry pre-sulfiding or wet process.
4. the start-up method of sulfurized hydrogenation catalyst described in accordance with the claim 3, wherein the wet process vulcanization is after airtight
Introducing goes into operation oil, and the oil that goes into operation is direct steaming gasoline, one kind of virgin kerosene and straight-run diesel oil.
5. the start-up method of sulfurized hydrogenation catalyst described in accordance with the claim 1, wherein the organic sulfur compound is sulphur
One or more of alcohol, carbon disulfide, dimethyl disulfide (DMDS), dimethyl sulfide, thioether, polysulfide.
6. the start-up method of sulfurized hydrogenation catalyst described in accordance with the claim 1, wherein the organic compound is four
Methylol microcosmic salt and its homologue.
7. the start-up method of sulfurized hydrogenation catalyst described in accordance with the claim 1, wherein the organic compound is four
One or more of methylol phosphorus chloride and its homologue, tetrakis hydroxymetyl phosphonium sulfuric and its homologue.
8. the start-up method of sulfurized hydrogenation catalyst described in accordance with the claim 1, wherein the organic compound is four
Ethoxy phosphorus chloride, tetrahydroxy aniline methyl chloride phosphorus, tetrahydroxy benzene methyl chloride phosphorus, tetrahydroxypropyl phosphorus chloride, tetrahydroxy
Vinylimidazolium chloride phosphorus, four hydroxyethyl methyl sulfuric acid phosphorus, tetrahydroxy aniline methylsulfuric acid phosphorus, tetrahydroxy benzene methylsulfuric acid phosphorus, four hydroxyls
Base propyl sulfuric acid phosphorus, one or more of tetrahydroxy vinylsulfuric acid phosphorus.
9. the start-up method of sulfurized hydrogenation catalyst described in accordance with the claim 1, wherein the hydrogenation catalyst is with resistance to
Molten inorganic oxide is carrier, and active metal component is generally one or more of W, Mo, Ni and Co.
10. the start-up method of sulfurized hydrogenation catalyst described in accordance with the claim 1, wherein the organic sulfur compound dosage
The 85%~150% of sulfur content, preferably 95%~120% is needed for hydrogenation catalyst metal component theory.
11. the start-up method of sulfurized hydrogenation catalyst described in accordance with the claim 1, wherein the organic compound dosage
It is the 2%~50% of catalyst weight, preferably 5%~30%.
12. the start-up method of sulfurized hydrogenation catalyst described in accordance with the claim 1, wherein the dosage of the hydrazine hydrate is
The 20% ~ 120% of organic sulfur compound dosage, preferably 30 ~ 80%.
13. the start-up method of sulfurized hydrogenation catalyst described in accordance with the claim 1, wherein the sulfide type catalyst group
The preparation method for closing object includes the following steps: the organic compound, organic sulfur compound and hydrazine hydrate while being introduced into catalysis
In agent, or substep is introduced on catalyst, includes at least one during introducing organic compound, organic sulfur compound and hydrazine hydrate
A Low Temperature Heat Treatment step and do not include calcination steps.
14. the start-up method of sulfurized hydrogenation catalyst according to claim 13, wherein the sulfide type catalyst group
Close the preparation method of object one of in the following way, (1) introduces organic sulfur compound, hydrazine hydrate and organic compound respectively,
It introduces and carries out Low Temperature Heat Treatment after every kind of component, the sequencing for introducing three kinds of substances is arbitrary；(2) by organic sulfide
Object, hydrazine hydrate and organic compound are made into homogeneous solution, Low Temperature Heat Treatment after impregnation catalyst agent；(3) organic sulfur compound is first introduced
And hydrazine hydrate, Low Temperature Heat Treatment, it is re-introduced into organic compound, Low Temperature Heat Treatment；(4) organic compound is first introduced, at Low Temperature Thermal
Reason, is re-introduced into organic sulfur compound and hydrazine hydrate, Low Temperature Heat Treatment.
15. the start-up method of sulfurized hydrogenation catalyst according to claim 13, wherein the temperature of the Low Temperature Heat Treatment
Degree be 20~200 DEG C, preferably 60~160 DEG C, the time be 1~for 24 hours, preferably 3~12h.
16. the start-up method of sulfurized hydrogenation catalyst according to claim 13, wherein the Low Temperature Heat Treatment can be
It is carried out under air, nitrogen or inert gas atmosphere.
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|---|---|---|---|---|
| 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 |
| CN112742487A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Start-up method of pre-vulcanized hydrogenation catalyst |
| CN114160168A (en) * | 2020-09-11 | 2022-03-11 | 中国石油化工股份有限公司 | Sulfurizing method of gasoline selective hydrogenation catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5338717A (en) * | 1990-12-24 | 1994-08-16 | Exxon Research And Engineering Company | Method for the preparation of supported hydrogenation and hydrotreating catalysts |
| CN106807406A (en) * | 2015-11-27 | 2017-06-09 | 中国石油天然气股份有限公司 | A kind of preparation method of molybdenum disulfide nano catalyst and catalyst and its application |
-
2017
- 2017-12-15 CN CN201711349792.3A patent/CN109926100B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5338717A (en) * | 1990-12-24 | 1994-08-16 | Exxon Research And Engineering Company | Method for the preparation of supported hydrogenation and hydrotreating catalysts |
| CN106807406A (en) * | 2015-11-27 | 2017-06-09 | 中国石油天然气股份有限公司 | A kind of preparation method of molybdenum disulfide nano catalyst and catalyst and its application |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112742487A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Start-up method of pre-vulcanized hydrogenation catalyst |
| CN112742487B (en) * | 2019-10-29 | 2023-02-03 | 中国石油化工股份有限公司 | Start-up method of pre-vulcanized hydrogenation catalyst |
| CN114160168A (en) * | 2020-09-11 | 2022-03-11 | 中国石油化工股份有限公司 | Sulfurizing method of gasoline selective hydrogenation catalyst |
| CN114160168B (en) * | 2020-09-11 | 2023-09-01 | 中国石油化工股份有限公司 | Sulfuration method of gasoline selective hydrogenation catalyst |
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