CN109926100B - Startup method of vulcanized hydrogenation catalyst - Google Patents
Startup method of vulcanized hydrogenation catalyst Download PDFInfo
- Publication number
- CN109926100B CN109926100B CN201711349792.3A CN201711349792A CN109926100B CN 109926100 B CN109926100 B CN 109926100B CN 201711349792 A CN201711349792 A CN 201711349792A CN 109926100 B CN109926100 B CN 109926100B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hydrogenation catalyst
- pressure
- low
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a startup method of a vulcanized hydrogenation catalyst, which comprises the following steps: filling the vulcanization type hydrogenation catalyst composition into a reactor, carrying out nitrogen gas tightness, gradually introducing hydrogen after the nitrogen gas tightness is qualified, carrying out hydrogen low-pressure gas tightness, and heating and boosting to carry out high-pressure gas tightness after the low-pressure gas tightness is qualified; and after the high-pressure airtight condition is qualified, adjusting the pressure to the reaction pressure until vulcanization is completed, finally adjusting the temperature to the reaction temperature, and starting hydrogenation reaction on the raw oil. The start-up method can ensure the vulcanization quality of the catalyst, solve the problem of air tightness of the device, and has no pollution to the environment, economy and environmental protection.
Description
Technical Field
The invention relates to a startup method of a catalyst, in particular to a startup method of a hydrogenation catalyst.
Background
In recent years, the crude oil deterioration tendency is increasingly obvious, the requirement of each country for clean fuel is increasingly increased, the hydrogenation process is taken as one of the most effective means for producing the clean fuel, and the high-efficiency hydrogenation catalyst becomes the technical key of the hydrogenation process. The active metal of the conventional hydrogenation catalyst is in an oxidation state, and the material which really plays an active role in actual use is in a vulcanization state, so the material needs to be vulcanized in a reactor before use.
The conventional hydrogenation catalyst is in an oxidation state, and substances which really play an active role in actual use are in a vulcanization state, so the conventional hydrogenation catalyst needs to be vulcanized in a reactor before being used. A typical in-situ presulfurization method is described in patent CN1171430A, wherein a vulcanizing agent is selected from carbon disulfide or dimethyl disulfide, the volume ratio of vulcanizing agent gas to a catalyst is generally 300-600, the vulcanization is carried out under normal pressure or high pressure, the general temperature raising and constant temperature procedure is to vulcanize for 2-6 hours at 200-240 ℃, and then vulcanize for 8-12 hours at 320-360 ℃. Because the in-situ prevulcanization is carried out in a refinery and special equipment is needed, the production cost is increased, and the vulcanization easily causes pollution to people and environment, so that scientific researchers at home and abroad actively seek a solution, and the ex-situ prevulcanization is carried forward.
By ex-situ presulfiding is meant that the catalyst is combined with a sulfiding agent prior to charging into the reactor and then charging into the reactor. During the start-up, H needs to be introduced2As the temperature increases, the sulfidizing agent decomposes to form hydrogen sulfide, thereby converting the hydrogenation-active metal to sulfide. CN1362493A discloses a vulcanization method of heavy oil hydrotreating catalyst, which is characterized in that solid sulfide is mixed with the catalyst, and a means of combining low-temperature dry vulcanization and high-temperature wet vulcanization is adopted, so as to prepare the vulcanization type catalyst. Compared with in-situ vulcanization, the ex-situ prevulcanization technology has the advantages of short start-up time, simple start-up steps, less investment on refinery equipment, less harm to human, less environmental pollution and the like. CN200910204284.5 discloses a method for starting a residual oil hydrogenation process, which comprises pre-sulfurizing a selected catalyst outside a reactor according to the requirements of the residual oil hydrogenation process, loading the catalyst into the reactor, heating, activating, and switching the residual oil raw material for hydrogenation treatment. The method only carries out ex-situ presulfurization treatment on part of the catalyst required by the residual oil hydrogenation process, saves the production cost and reduces the catalyst loss while maintaining the advantages of the ex-situ presulfurization process. The prevulcanization raw materials of the two patents are solid sulfur, the decomposition temperature is about 100 ℃ under hydrogen, and due to the limitation of reactor materials of a hydrogenation device, production safety and other aspects, the high-pressure air tightness of the device needs to be carried out at the lowest temperature of the whole device to reach 92 ℃, so that the inlet temperature of the reactor reaches at least above 150 ℃, and the vulcanization reaction starts before the high-temperature air tightness of the device. Hydrogen sulfide enters the circulating hydrogen before airtight sealing, and once the airtight sealing is unqualified and the air is emptied, the vulcanizing agent is insufficient, so that the vulcanizing effect of the catalyst is influenced. Therefore, the air tightness problem of the device becomes a difficult problem to be solved urgently in the application and popularization of the external prevulcanization technology at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a start-up method of a vulcanization type hydrogenation catalyst, wherein during vulcanization of a catalyst composition used in the start-up process, an organic sulfide, an organic compound and hydrazine hydrate form an intermediate fixed sulfide at a low temperature, so that the airtightness of the device is smoothly carried out, after the temperature is raised to a certain height, the organic compound and the organic sulfide are decomposed, and the organic sulfide reacts with hydrogen and metal to carry out vulcanization of the catalyst. The catalyst does not need an additional vulcanizing agent during startup vulcanization, so that the vulcanization quality of the catalyst can be ensured, and the problem of air tightness of the device can be solved.
Aiming at the defects in the prior art, the invention provides a start-up method of a vulcanized hydrogenation catalyst, which comprises the following steps:
(1) loading the sulfuration type hydrogenation catalyst composition into a reactor, and sealing with nitrogen;
(2) introducing hydrogen gradually after the nitrogen gas tightness is qualified, carrying out low-pressure gas tightness on the hydrogen, heating after the low-pressure gas tightness is qualified, and boosting the pressure to carry out high-pressure gas tightness when the inlet temperature of the reactor is 130-180 ℃;
(3) after the high-pressure airtight is qualified, adjusting the pressure to the reaction pressure, then continuously heating to 200-250 ℃, continuously heating to 270-320 ℃ after 3-12 h of vulcanization, and vulcanizing for 3-24 h until the vulcanization is finished;
(4) adjusting the temperature to the reaction temperature, and starting hydrogenation reaction of the raw oil;
wherein the sulfided hydrogenation catalyst composition comprises:
(1) an oxidation state hydrogenation catalyst;
(2) organic sulfide, wherein the dosage of the organic sulfide is 85-150%, preferably 95-120% of the theoretical sulfur demand of the metal component of the hydrogenation catalyst;
(3) an organic compound in an amount of 2 to 50%, preferably 5 to 30% by weight of the catalyst.
(4) Hydrazine hydrate, wherein the using amount of the hydrazine hydrate is 20-120% of that of the organic sulfide, and preferably 30-80%.
In the start-up method, the pressure in the step (2) during low-pressure airtight sealing is 1.0-3.0 MPa, and the pressure during high-pressure airtight sealing is 120-200% of the reaction pressure, based on the operation pressure of a specific device. In the start-up method of the present invention, the airtight pressure and temperature are required to strictly comply with the requirements of the pressure vessel in order to ensure the safety of the hydrogenation apparatus, and the specific operation method is well known to those skilled in the art.
In the start-up method of the present invention, the hydrogenation reaction conditions in step (4), such as reaction pressure, temperature, hydrogen-oil ratio, space velocity, etc., are determined by those skilled in the art according to the properties of the raw oil to be reacted, the requirements of the desired product, and the performance of the catalyst. The general reaction pressure is 1.0-20.0 MPa, the temperature is 150-450 ℃, the hydrogen-oil ratio is 200-2000, and the space velocity is 1.0-10.0 h-1. The raw oil can be various hydrogenated raw materials and mixtures thereof.
In the start-up method, after the high-pressure airtightness is qualified, dry vulcanization can be adopted, oil is not fed in the vulcanization process, and wet vulcanization can also be used, wherein start-up oil is introduced after airtightness is realized by the wet vulcanization, and the start-up oil is one of straight-run gasoline, straight-run kerosene and straight-run diesel oil.
In the above-mentioned start-up method, the organic sulfide is a vulcanizing agent conventionally used in the art, and may be one or more of sulfur-containing organic compounds. The organic sulfide can be one or more of mercaptan, carbon disulfide, dimethyl disulfide (DMDS), dimethyl sulfide, and polysulfide selected from the group consisting of compounds of the general formula R-Sn-one or more organic polysulphides of R ', n being 2 to 10, R and R ' being identical or different and being saturated or unsaturated, linear or branched, cycloalkyl or aromatic, and the number of carbon atoms of R and R ' being 1 to 10.
In the above-mentioned method of operation, the organic compound is tetrakis (hydroxymethyl) phosphonium salt and its homologues, specifically may be one or more of tetrakis (hydroxymethyl) phosphonium chloride and its homologues, tetrakis (hydroxymethyl) phosphonium sulfate and its homologues, the substituted hydrocarbons may be the same or different, and may be saturated or unsaturated, straight-chain or branched, cycloalkyl or aryl, and the number of carbon atoms of the hydrocarbons may be 1-10. Specifically, the phosphorus chloride may be one or more of tetrahydroxyethyl phosphorus chloride, tetrahydroxylaniline methyl phosphorus chloride, tetrahydroxybenzyl phosphorus chloride, tetrahydroxypropyl phosphorus chloride, tetrahydroxyvinyl phosphorus chloride, tetrahydroxyethyl methyl phosphorus sulfate, tetrahydroxylaniline methyl phosphorus sulfate, tetrahydroxybenzyl phosphorus sulfate, tetrahydroxypropyl phosphorus sulfate, and tetrahydroxyvinyl phosphorus sulfate.
In the start-up method, the hydrogenation catalyst is any one of a hydrofining catalyst, a hydrocracking catalyst and a hydrotreating catalyst. Refractory inorganic oxide is generally used as a carrier, such as alumina, silica, amorphous silica-alumina, titania, a molecular sieve, and composite oxides of various elements or mixed oxygen carriers, and the active metal component is generally one or more of W, Mo, Ni and Co, and may contain an auxiliary agent. The selection and the dosage of the hydrogenation catalyst carrier, the active metal component and the auxiliary agent can be specifically determined according to the application requirements according to general knowledge in the field, and for the hydrocarbon hydrogenation catalyst, the content of the hydrogenation metal component calculated by oxide is generally 1-90% of the weight of the catalyst, and is usually 3-50%. The theoretical sulfur demand of the hydrogenation catalyst is that the metal components contained in the catalyst are converted into sulfide (Co)9S8、MoS2、Ni3S2、WS2) The amount of sulfur is needed.
In the above start-up method, the preparation method of the sulfided catalyst composition comprises the steps of: the organic compound, organic sulfide and hydrazine hydrate are introduced onto the catalyst simultaneously or in steps, including at least one low temperature heat treatment step and not including a calcination step during the introduction of the organic compound, organic sulfide and hydrazine hydrate. Specifically, the method can adopt the following modes that (1) organic sulfide, hydrazine hydrate and organic compound are respectively introduced, low-temperature heat treatment is carried out after each component is introduced, and the sequence of introducing the three substances can be arbitrary; (2) preparing organic sulfide, hydrazine hydrate and organic compound into a uniform solution, and performing low-temperature heat treatment after dipping a catalyst; (3) firstly introducing organic sulfide and hydrazine hydrate, carrying out low-temperature heat treatment, then introducing an organic compound, and carrying out low-temperature heat treatment. (4) Firstly introducing organic compound, low-temperature heat treatment, then introducing organic sulfide and hydrazine hydrate, and low-temperature heat treatment.
In the preparation method of the hydrotreating catalyst composition, the temperature of the low-temperature heat treatment is 20-200 ℃, preferably 60-160 ℃, and the time is 1-24 hours, preferably 3-12 hours.
In the above method for preparing the hydroprocessing catalyst composition, the low-temperature heat treatment may be carried out under an atmosphere of air, nitrogen or inert gas.
Compared with the prior art, the start-up method has the following advantages:
1. the invention adopts a brand new start-up method, perfectly solves the problems of high-temperature air tightness of the device and low-temperature overflow of the vulcanizing agent when the pre-vulcanized catalyst outside the device is started, organic compounds and organic sulfides form intermediates at low temperature in the vulcanization process of the catalyst, the sulfides are fixed, the overflow of the vulcanizing agent is inhibited, the high-temperature air tightness of the device is smoothly carried out, the intermediates formed by the organic compounds and the sulfides are decomposed after the temperature rises to a certain height, and the organic sulfides react with hydrogen and metals to carry out the vulcanization of the catalyst, thereby not only ensuring the vulcanization quality of the catalyst, but also solving the air tightness problem of the device.
2. The organic compound in the catalyst composition and the organic sulfide can form an intermediate in the preparation process of the ex-situ presulfurization catalyst under the action of hydrazine hydrate, and the generated intermediate is uniformly loaded on the surface and in pore channels of the catalyst, so that the catalyst is uniformly and thoroughly sulfurized, and the hydrogenation activity of the catalyst is favorably improved. The organic compound is matched with various organic sulfides, so that exothermic peaks of a vulcanization reaction can be dispersed, and temperature runaway of a bed layer can be avoided.
Detailed Description
The technical features of the present invention will be further described below by way of examples, which are not intended to limit the present invention.
Example 1
(1) Preparation of hydrogenation catalyst A
Taking 100g of oxidation state catalyst for industrial production, taking 10ml of mixed DMDS18g and hydrazine hydrate, spraying the catalyst, putting a sample into a forced air drying oven for first low-temperature heat treatment, wherein the conditions of the first low-temperature heat treatment are as follows: the temperature is raised to 80 ℃ at the speed of 3 ℃/min, and the temperature is kept for 3 hours. And (3) spraying 50g of tetrakis (hydroxymethyl) phosphonium sulfate aqueous solution (75wt%) on the sample subjected to the first low-temperature heat treatment, and putting the sample into a forced air drying oven for second low-temperature heat treatment after spraying, wherein the conditions of the second low-temperature heat treatment are the same as those of the first low-temperature heat treatment, so as to obtain the hydrotreating catalyst A.
(2) Catalyst start-up method and evaluation
Loading a vulcanization type hydrogenation catalyst into a reactor, and sealing with nitrogen; introducing hydrogen gradually after the nitrogen gas tightness is qualified, carrying out hydrogen low-pressure gas tightness with the gas tightness pressure of 2.0MPa, igniting and heating a heating furnace after the gas tightness is qualified, starting boosting the pressure to carry out high-pressure gas tightness when the temperature of the reactor inlet is 150 ℃, reducing the pressure to the reaction pressure of 7.2MPa after the high-pressure gas tightness is qualified, introducing start-up oil straight-run diesel oil, keeping the temperature for 4 hours, then continuously raising the temperature to 200 ℃, keeping the temperature for 8 hours for vulcanization, then continuously raising the temperature to 280 ℃, and keeping the temperature for 8 hours for vulcanization. Catalytic diesel oil is added, the temperature is continuously raised to 350 ℃ of reaction temperature, and sampling analysis is carried out after the constant temperature is kept for 8 hours. The tail gas is sampled and analyzed in the vulcanization process, and the contents of hydrogen sulfide and sulfide are shown in tables 1 and 2. The reaction conditions of the catalytic diesel oil are as follows: the pressure is 7.2MPa, the space velocity is 1.5, the temperature is 350 ℃, and the hydrogen-oil ratio is 1000. The density of the catalytic diesel oil is 0.890g/cm3The sulfur content was 10453. mu.g/g, the nitrogen content was 852. mu.g/g, and the evaluation results are shown in Table 3.
Example 2
(1) Preparation of hydrogenation catalyst B
Taking 100g of industrially produced oxidation state catalyst, taking 10ml of mixed solution of DMDS18g and hydrazine hydrate and 50g of tetrakis (hydroxymethyl) phosphonium sulfate aqueous solution (the solution concentration is 75wt%), spraying the catalyst in parallel flow, and then putting the sample into a forced air drying oven for low-temperature heat treatment, wherein the low-temperature heat treatment conditions are as follows: the temperature is raised to 80 ℃ at the speed of 3 ℃/min, and the temperature is kept for 3 hours. Thus obtaining the hydrotreating catalyst B.
(2) Catalyst start-up method and evaluation
The catalyst start-up method and evaluation were the same as in step (2) of example 1, and the contents of hydrogen sulfide and sulfide were shown in tables 1 and 2. The evaluation results are shown in Table 3.
Example 3
(1) Preparation of hydrogenation catalyst C
Taking 100g of an oxidation state catalyst for industrial production, taking 13g of carbon disulfide and 12ml of hydrazine hydrate, mixing, then adding 65ml of a tetrahydroxyethyl phosphorus sulfate aqueous solution, stirring for 20min to form a uniform solution spray catalyst, putting a sample into a forced air drying oven for low-temperature heat treatment, wherein the treatment conditions are as follows: the temperature is raised to 80 ℃ at the speed of 3 ℃/min, and the temperature is kept for 3 hours. Thus obtaining the hydrotreating catalyst C.
(2) Catalyst start-up method and evaluation
Loading a vulcanization type hydrogenation catalyst into a reactor, and sealing with nitrogen; introducing hydrogen gradually after the nitrogen gas tightness is qualified, carrying out hydrogen low-pressure gas tightness with the gas tightness pressure of 2.0MPa, igniting and heating a heating furnace after the gas tightness is qualified, starting boosting the pressure to carry out high-pressure gas tightness when the temperature of the reactor inlet is 150 ℃, keeping the gas tightness pressure at 10MPa, reducing the pressure to the reaction pressure of 7.2MPa after the high-pressure gas tightness is qualified, continuously heating to 200 ℃, keeping the temperature for 8 hours for vulcanization, then continuously heating to 280 ℃, and keeping the temperature for 8 hours to finish the vulcanization. Introducing catalytic diesel oil, continuously heating to the reaction temperature of 350 ℃, keeping the temperature for 8 hours, and then sampling and analyzing. The tail gas is sampled and analyzed in the vulcanization process, and the contents of hydrogen sulfide and sulfide are shown in tables 1 and 2. The feed oil and process conditions were the same as in step (2) of example 1. The evaluation results are shown in Table 3.
Example 4
(1) Preparation of hydrogenation catalyst D
Taking 100g of oxidation state catalyst for industrial production, mixing DMDS9g and 13g of dimethyl sulfoxide, mixing with 10ml of hydrazine hydrate, spraying the catalyst, and putting a sample into a forced air drying oven for first low-temperature heat treatment, wherein the conditions of the first low-temperature heat treatment are as follows: the temperature is raised to 100 ℃ at the speed of 3 ℃/min, and the temperature is kept for 3 hours. Taking 17g of tetrakis (hydroxymethyl) phosphonium chloride, diluting with 50g of water, spraying the sample subjected to the first low-temperature heat treatment, putting the sample into a forced air drying oven after spraying, and performing second low-temperature heat treatment, wherein the second low-temperature heat treatment condition is that the temperature is increased to 120 ℃ at the speed of 3 ℃/min, and the temperature is kept constant for 3 hours. Thus obtaining the hydrotreating catalyst D.
(2) Catalyst start-up method and evaluation
The catalyst start-up method and evaluation were the same as in step (2) of example 1, and the contents of hydrogen sulfide and sulfide were shown in tables 1 and 2. The evaluation results are shown in Table 3.
Example 5
(1) Preparation of hydrogenation catalyst E
Taking 100g of oxidation state catalyst for industrial production, taking 10ml of mixed DMDS18g and hydrazine hydrate, spraying the catalyst, putting a sample into a forced air drying oven for first low-temperature heat treatment, wherein the conditions of the first low-temperature heat treatment are as follows: the temperature is raised to 80 ℃ at the speed of 3 ℃/min, and the temperature is kept for 3 hours. And (3) taking 36g of tetrahydroxytoluidine-based phosphorus chloride, diluting with 50g of water, spraying the sample subjected to the first low-temperature heat treatment, putting the sample into a forced air drying oven after spraying, and performing second low-temperature heat treatment under the same conditions as the first low-temperature heat treatment to obtain the hydrotreating catalyst E.
(2) Catalyst start-up method and evaluation
The catalyst start-up method and evaluation were the same as in the step (2) of example 1, and the contents of hydrogen sulfide and sulfide were shown in tables 1 and 2, and the evaluation results were shown in table 3.
Comparative example 1
(1) Preparation of hydrogenation catalyst F
Taking 100g of an oxidation state catalyst for industrial production, taking DMDS18g for spraying, and then putting a sample into a forced air drying oven for low-temperature heat treatment, wherein the conditions of the low-temperature heat treatment are as follows: the temperature is raised to 120 ℃ at the speed of 3 ℃/min, and the temperature is kept for 3 hours. Thus obtaining the hydrotreating catalyst F.
(2) Catalyst start-up method and evaluation
The catalyst start-up method and evaluation were the same as in the step (2) of example 1, and the contents of hydrogen sulfide and sulfide were shown in tables 1 and 2, and the evaluation results were shown in table 3.
Comparative example 2
(1) Preparation of hydrogenation catalyst G
Taking 100g of oxidation state catalyst for industrial production, taking 13g of carbon disulfide, spraying, and then putting a sample into a blast drying oven for low-temperature heat treatment, wherein the conditions of the first low-temperature heat treatment are as follows: the temperature is raised to 80 ℃ at the speed of 3 ℃/min, and the temperature is kept for 3 hours. Thus obtaining the hydrotreating catalyst G.
(2) Catalyst start-up method and evaluation
The catalyst start-up method and evaluation were the same as in the step (2) of example 1, and the contents of hydrogen sulfide and sulfide were shown in tables 1 and 2, and the evaluation results were shown in table 3.
Comparative example 3
(1) Preparation of hydrogenation catalyst H
Same as example 1 except that hydrazine hydrate was added. To obtain the catalyst H.
(2) Catalyst start-up method and evaluation
The catalyst start-up method and evaluation were the same as in the step (2) of example 1, and the contents of hydrogen sulfide and sulfide were shown in tables 1 and 2, and the evaluation results were shown in table 3.
Comparative example 4
(1) Preparation of hydrogenation catalyst J
Taking 100g of oxidation state catalyst in industrial production, taking 13g of carbon disulfide as spray catalyst, aging for 2 hours, taking 65ml of tetrahydroxy ethyl phosphoric sulfate aqueous solution (containing 36g of tetrahydroxy ethyl phosphoric sulfate) as spray catalyst, putting the sample into a forced air drying oven for low-temperature heat treatment, wherein the treatment conditions are as follows: the temperature is raised to 80 ℃ at the speed of 3 ℃/min, and the temperature is kept for 3 hours. Thus obtaining the hydrotreating catalyst J.
(2) Catalyst start-up method and evaluation
The catalyst start-up method and evaluation were the same as in the step (2) of example 1, and the contents of hydrogen sulfide and sulfide were shown in tables 1 and 2, and the evaluation results were shown in table 3.
Test example 1 evaluation of Activity of Oxidation-type hydrogenation catalyst
Taking the oxidation state catalyst used in the experiment for activity stability evaluation, wherein the airtight process is the same as the step (2) of the example 1, the reaction pressure is reduced to 7.2MPa after the airtight is qualified, and the vulcanized oil is started to be fed, wherein the vulcanized oil is a mixture of aviation kerosene and carbon disulfide, and the density of the vulcanized oil is 0.798g/cm3The sulfur content is 20000 mu g/g, the nitrogen content is 1.0 mu g/g, and the distillation range is 161-276 ℃. Keeping the temperature for 4 hours, raising the temperature to 230 ℃ at the temperature rise speed of 20 ℃/h, keeping the temperature for 8 hours, raising the temperature to 320 ℃, keeping the temperature for 8 hours, and finishing vulcanization. Then catalytic diesel oil is added, the temperature is raised to 350 ℃, and the temperature is kept for 8 hours, and then sampling analysis is carried out.The tail gas is sampled and analyzed in the vulcanization process, and the contents of hydrogen sulfide and sulfide are shown in tables 1 and 2. The feed oil and process conditions were the same as in step (2) of example 1. The evaluation results are shown in Table 3.
TABLE 1 analysis results of sulfides in exhaust gas (sulfides other than hydrogen sulfide)
TABLE 2 analysis of hydrogen sulfide in tail gas
TABLE 3 evaluation results of catalysts
As can be seen from tables 1 and 2, the organic sulfide is directly loaded on the catalyst, and when the temperature is low, namely 120-130 ℃, the sulfide overflows from the catalyst pore channels, while the high-pressure air tightness of the device is generally 150 ℃, if the air tightness is unqualified, the vulcanizing agent is lost when the air tightness is emptied, so that the subsequent metal vulcanization is incomplete, and the activity of the catalyst is influenced. The organic compound and the organic sulfide in the catalyst are adsorbed and complexed under the action of hydrazine hydrate and are uniformly loaded on the surface and in the pore channels of the catalyst, the complex formed by the organic compound and the organic sulfide at the low temperature of less than 180 ℃ does not decompose when the catalyst is vulcanized, the sulfide is fixed, the reaction of the complex with hydrogen is hindered, the high-temperature air tightness of the device is smoothly carried out, when the temperature rises to 180 ℃, the organic compound and the sulfide are decomplexed, and the sulfide reacts with the hydrogen and metal to carry out the vulcanization of the catalyst, so that the vulcanization quality of the catalyst can be ensured, and the problem of air tightness of the device can be solved. As can be seen from table 3, the catalyst has high hydrogenation activity, and the preparation process of the catalyst is simple and economical. The catalyst is a vulcanization type catalyst, the start-up process is simple, and the time required by start-up is greatly reduced.
Claims (16)
1. A start-up method of a vulcanized hydrogenation catalyst comprises the following steps:
(1) loading the sulfuration type hydrogenation catalyst composition into a reactor, and sealing with nitrogen;
(2) introducing hydrogen gradually after the nitrogen gas tightness is qualified, carrying out low-pressure gas tightness on the hydrogen, heating after the low-pressure gas tightness is qualified, and boosting the pressure to carry out high-pressure gas tightness when the inlet temperature of the reactor is 130-180 ℃;
(3) after the high-pressure airtight is qualified, adjusting the pressure to the reaction pressure, then continuously heating to 200-250 ℃, continuously heating to 270-320 ℃ after 3-12 h of vulcanization, and vulcanizing for 3-24 h until the vulcanization is finished;
(4) adjusting the temperature to the reaction temperature, and starting hydrogenation reaction of the raw oil;
wherein the sulfided hydrogenation catalyst composition comprises: an oxidation state hydrogenation catalyst, an organic sulfide, an organic compound and hydrazine hydrate; the organic compound is one or more of tetrakis hydroxymethyl phosphonium chloride and homologues thereof, and tetrakis hydroxymethyl phosphonium sulfate and homologues thereof; the organic sulfide is one or more of mercaptan, carbon disulfide, dimethyl sulfide, thioether and polysulfide, the polysulfide is selected from one or more of organic polysulfides with a general formula of R-Sn-R ', the value of n is 2-10, R and R ' are the same or different and are saturated or unsaturated, straight chain or branched chain, naphthenic base or aromatic base, and the number of carbon atoms of R and R ' is 1-10;
the preparation method of the sulfurized catalyst composition comprises the following steps: the organic compound, organic sulfide and hydrazine hydrate are introduced onto the catalyst simultaneously or in steps, including at least one low temperature heat treatment step and not including a calcination step during the introduction of the organic compound, organic sulfide and hydrazine hydrate.
2. The method for starting up a sulfided hydrogenation catalyst as recited in claim 1, wherein the pressure at low pressure and at high pressure in step (2) is 1.0 to 3.0MPa, and the pressure at high pressure and at high pressure is 120 to 200% of the reaction pressure, based on the operation pressure of the specific apparatus.
3. The method for starting up a sulfided hydrogenation catalyst as recited in claim 1, wherein the dry sulfiding or wet sulfiding is employed after the high pressure gas tight seal is passed.
4. The method of starting up a sulfided hydroprocessing catalyst as recited in claim 3, wherein said wet sulfiding introduces a start-up oil after gas seal, the start-up oil being one of straight run gasoline, straight run kerosene and straight run diesel.
5. The method for starting up a sulfided hydrogenation catalyst as claimed in claim 1, wherein the organic compound is one or more of tetrakis hydroxymethyl phosphonium chloride, tetrakis hydroxyethyl phosphonium chloride, tetrakis hydroxypropyl phosphonium chloride, tetrakis hydroxymethyl phosphonium sulfate, and tetrakis hydroxypropyl phosphonium sulfate.
6. The method for starting up a sulfided hydrogenation catalyst as claimed in claim 1, wherein the hydrogenation catalyst uses refractory inorganic oxide as a carrier, and the active metal component is one or more of W, Mo, Ni and Co.
7. The method for starting up a sulfided hydrogenation catalyst as recited in claim 1, wherein the amount of said organosulfide is 85% to 150% of the theoretical sulfur requirement of the metal component of the hydrogenation catalyst.
8. The method for starting up a sulfided hydrogenation catalyst as recited in claim 1 or 7, wherein the amount of the organic sulfide is 95% to 120% of the theoretical sulfur demand of the metal component of the hydrogenation catalyst.
9. The process for the start-up of a sulfided hydrogenation catalyst as described in claim 1, wherein the organic compound is present in an amount of 2% to 50% by weight of the catalyst.
10. A process for the start-up of a sulphided hydrogenation catalyst according to claim 1 or 9 wherein the organic compound is used in an amount of from 5 to 30% by weight of the catalyst.
11. The startup method of the sulfurized hydrogenation catalyst as defined in claim 1, wherein the amount of hydrazine hydrate is 20-120% of the amount of organic sulfide.
12. The method for starting up a sulfided hydrogenation catalyst as described in claim 1 or 11, wherein the amount of hydrazine hydrate is 30 to 80% of the amount of organic sulfide.
13. The start-up method for a sulfided hydrogenation catalyst as described in claim 1, wherein the sulfided catalyst composition is prepared by one of (1) separately introducing an organosulfide, a hydrazine hydrate, and an organic compound, and after each component is introduced, performing a low temperature heat treatment, the order of introduction of the three is arbitrary; (2) preparing organic sulfide, hydrazine hydrate and organic compound into a uniform solution, and performing low-temperature heat treatment after dipping a catalyst; (3) firstly, introducing organic sulfide and hydrazine hydrate, carrying out low-temperature heat treatment, then introducing an organic compound, and carrying out low-temperature heat treatment; (4) firstly introducing organic compound, low-temperature heat treatment, then introducing organic sulfide and hydrazine hydrate, and low-temperature heat treatment.
14. The startup method of the sulfided hydrogenation catalyst as described in claim 13, wherein the temperature of the low-temperature heat treatment is 20 to 200 ℃ and the time is 1 to 24 hours.
15. The startup method of the sulfided hydrogenation catalyst as described in claim 13, wherein the temperature of the low-temperature heat treatment is 60 to 160 ℃ and the time is 3 to 12 hours.
16. The method for starting up a sulfided hydrogenation catalyst as described in claim 13, wherein said low temperature heat treatment is carried out under air, nitrogen or inert gas atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711349792.3A CN109926100B (en) | 2017-12-15 | 2017-12-15 | Startup method of vulcanized hydrogenation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711349792.3A CN109926100B (en) | 2017-12-15 | 2017-12-15 | Startup method of vulcanized hydrogenation catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109926100A CN109926100A (en) | 2019-06-25 |
| CN109926100B true CN109926100B (en) | 2021-10-08 |
Family
ID=66979951
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711349792.3A Active CN109926100B (en) | 2017-12-15 | 2017-12-15 | Startup method of vulcanized hydrogenation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109926100B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109926100A (en) | 2019-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109926100B (en) | Startup method of vulcanized hydrogenation catalyst | |
| JPH08173824A (en) | Method for out-of-situ preliminary treatment of hydrocarbon treating catalyst | |
| CN109926103B (en) | Regeneration method of deactivated catalyst | |
| CN104593050B (en) | The start-up method of sulfurized hydrogenation catalyst | |
| JP2000117121A (en) | Ex-situ presulfurization in the presence of hydrocarbon molecule | |
| CN102051204B (en) | Work starting method for hydrogenation process | |
| CN1283361C (en) | In situ outer prevulcanization method for hydrogenation catalyst | |
| CN109926101B (en) | Startup method of vulcanized catalyst | |
| CN109926105B (en) | Regeneration method of hydrogenation catalyst | |
| CN105521791A (en) | Method for preparing sulfuration-type gasoline selective hydro-desulfurization catalyst | |
| CN1237150C (en) | Sulfurated hydrogenation catalyst and its preparing process | |
| CN102041045B (en) | On-stream method of residual oil hydrogenation process | |
| CN111068794B (en) | External presulfurization method of hydrogenation catalyst | |
| CN104593051B (en) | A kind of start-up method of sulfurized hydrogenation catalyst | |
| CN109777486B (en) | Hydrocracking start-up method | |
| CN109926097B (en) | Vulcanization type hydrogenation catalyst composition and preparation method thereof | |
| CN114950493A (en) | Molybdenum-based sulfide supported catalyst and in-situ preparation method and application thereof | |
| CN112742427B (en) | Startup method of hydrogenation catalyst | |
| CN112295575B (en) | Preparation method of hydrogenation catalyst and hydrogenation device startup method | |
| CN112705246A (en) | Desulfurization and dearomatization catalyst and preparation method thereof | |
| CN110508294B (en) | Preparation method of hydrogenation catalyst, hydrogenation catalyst prepared by method and application of hydrogenation catalyst | |
| CN102019209B (en) | Hydrocarbon processing catalysts is carried out the method for sulfuration | |
| CN109777474B (en) | Wet startup method for hydrocracking | |
| CN113856694B (en) | Sulfurized hydrogenation catalyst, and preparation method and application thereof | |
| CN106925356B (en) | Pre-sulfurizing method of hydrogenation catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230531 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |
|
| TR01 | Transfer of patent right |