CN112871219B - Flame-retardant composition for hydrogenation catalysis and use method thereof - Google Patents
Flame-retardant composition for hydrogenation catalysis and use method thereof Download PDFInfo
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- CN112871219B CN112871219B CN202110046515.5A CN202110046515A CN112871219B CN 112871219 B CN112871219 B CN 112871219B CN 202110046515 A CN202110046515 A CN 202110046515A CN 112871219 B CN112871219 B CN 112871219B
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Abstract
The invention relates to the technical field of hydrocracking, in particular to a flame-retardant composition for hydrogenation catalysis and a using method thereof, wherein the flame-retardant composition comprises 100 parts of a flame retardant, 5-15 parts of a film-forming assistant and 5-10 parts of a cosolvent. The flame retardant and the film-forming assistant are firstly mixed in the cosolvent, and when the flame retardant and the film-forming assistant are added into the mixed oil of diesel oil, wax oil and the like in the hydrogenation reactor, the flame retardant and the film-forming assistant can be quickly compatible, the dispersion of the flame retardant and the film-forming assistant is promoted, the mixed oil is cooperated, the film-forming rate on the catalyst is improved, a passivation film is formed at 170 ℃, and the agent unloading efficiency is improved; the penetrant is added to promote the internal action of the flame-retardant composition and the agglomerated catalyst, improve the uniformity and compactness of the passive film, improve the stability of the flame-retardant effect, promote the stability of the catalyst under the conditions of air or illumination and the like, and improve the safety of agent unloading and catalyst regeneration; after the gas is cooled and replaced by using the alcohol containing the aliphatic chain, the oil content of the catalyst is less than 5 percent, and the regeneration activity of the catalyst is not influenced.
Description
Technical Field
The invention relates to the technical field of hydrocracking, in particular to a flame-retardant composition for hydrogenation catalysis and a using method thereof.
Background
The hydrocracking technology is one of the most important secondary processing technologies in petroleum refining, has strong raw material adaptability and flexible product scheme, and can directly produce clean oil products with excellent quality in the process of petroleum lightening. The core of hydrocracking is a catalyst, and fixed bed hydrogenation catalysts such as hydrocracking, hydrofining and the like mostly contain metals such as nickel, cobalt, molybdenum, tungsten, iron and the like, and after reaction, the metals are generally in a highly sulfurized state, and in addition, due to the existence of coke, the catalysts are extremely easy to spontaneously combust. If the catalyst is not effectively pretreated or protected after the reaction, the metal sulfides are very easy to oxidize and spontaneously combust when being contacted with air in the agent unloading process, thereby causing accidents.
In order to prevent the catalyst from spontaneous combustion, measures such as in-reactor coke burning regeneration, inert gas (generally nitrogen) protection, water or soda water spraying and the like are adopted at present, but the methods not only have long time consumption and high cost, but also are easy to damage the catalyst, so that the regeneration activity of the catalyst is reduced, and the method of spraying the water or the soda water is only suitable for the scrapped catalyst.
With the increasing environmental protection requirements and the increasing quality requirements of oil products, many oil refining manufacturers increasingly build hydrogenation devices, and with the increasing requirements for safe agent discharge and regeneration of hydrogenation catalysts, research on flame retardants of hydrogenation catalysts is carried out at home and abroad at present, but good flame retardant effect and stability are difficult to obtain in industrial agent discharge, and regeneration activity of catalysts is affected.
Disclosure of Invention
In order to solve the problems, the first aspect of the invention provides a flame retardant composition for hydrogenation catalysis, and the flame retardant composition comprises, by weight, 100 parts of a flame retardant, 5-15 parts of a film-forming assistant and 5-10 parts of a cosolvent.
In a preferred embodiment of the present invention, the film-forming aid includes a quaternary ammonium salt, and the quaternary ammonium salt is at least one selected from alkyl quaternary ammonium salts, amido quaternary ammonium salts, and aryl quaternary ammonium salts.
In a preferred embodiment of the present invention, the quaternary ammonium salt is at least one selected from the group consisting of alkyl quaternary ammonium salts of C9-C20 and amido quaternary ammonium salts of C9-C20.
As a preferable technical scheme of the invention, the cosolvent is selected from one or more of diesel oil, wax oil and petroleum acid.
In a preferable technical scheme of the invention, the acid value of the petroleum acid is 175-210 mgKOH/g.
As a preferable technical solution of the present invention, the preparation raw material of the flame retardant composition further comprises a penetration enhancer, and the penetration enhancer is one or more selected from a pyridine salt, an imidazole salt, and an isoquinoline salt.
In a preferred embodiment of the invention, the permeation enhancer comprises at least one N-alkyl functional group.
In a preferred embodiment of the present invention, the N-alkyl functional group is an N- (C1-C6 alkyl) functional group.
As a preferable technical scheme, the permeation assistant agent accounts for 1-5 wt% of the flame retardant.
The second aspect of the present invention provides a method for using the flame retardant composition for hydrogenation catalysis, which comprises:
(1) cooling and reducing the temperature;
(2) wax oil displacement;
(3) diesel oil displacement;
(4) injecting a flame retardant composition;
(5) forming a film;
(6) and (5) cooling and replacing the gas.
Compared with the prior art, the invention has the following beneficial effects:
(1) the flame retardant composition for hydrogenation catalysis is provided, a flame retardant and a film-forming assistant are firstly mixed in a cosolvent, when the flame retardant and the film-forming assistant are added into mixed oil such as diesel oil, wax oil and the like in a hydrogenation reactor, the flame retardant and the film-forming assistant can be quickly compatible, the dispersion of the flame retardant and the film-forming assistant is promoted, the mixed oil is cooperated, the film-forming rate on a catalyst is improved, a firm passivation film is formed at 170 ℃, and the agent unloading efficiency is improved;
(2) the micromolecule penetrating agent, the flame retardant, the film forming auxiliary agent and the cosolvent are added to jointly act, so that the internal action of the flame-retardant composition and the agglomerated catalyst is promoted, the uniformity and compactness of a passivation film are improved, the stability of the flame-retardant effect is improved, the stability of the catalyst under the conditions of air or illumination and the like is promoted, and the safety of agent unloading and catalyst regeneration is improved;
(3) when the alcohol containing fatty chain is used together with other components of the composition, and the hydrogen or nitrogen is used for gas cooling replacement (also called oil removal), the oil content of the catalyst is less than 5 percent after the hydrogenation reactor is cooled from 170 ℃ to below 50 ℃, and the regeneration activity of the catalyst is not influenced.
(4) The flame-retardant composition used in the invention does not contain components such as aryl and the like, thereby avoiding environmental pollution and improving the operation safety of the discharging agent.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, this phrase shall render the claim closed except for the materials described except for those materials normally associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; no other elements are excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "either" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
The invention provides a flame-retardant composition for hydrogenation catalysis, which comprises 100 parts of a flame retardant, 5-15 parts of a film-forming assistant and 5-10 parts of a cosolvent in parts by weight.
In a preferred embodiment, the preparation raw materials of the flame retardant composition comprise, by weight, 100 parts of a flame retardant, 10-15 parts of a film-forming aid and 5-10 parts of a cosolvent.
In a preferred embodiment, the raw materials for preparing the flame-retardant composition comprise 100 parts of flame retardant, 12 parts of film-forming assistant and 6 parts of cosolvent in parts by weight.
Flame retardant
The flame retardant is a passivator used for preventing the catalyst from spontaneous combustion during the agent unloading of the hydrogenation unit. The catalyst is in a vulcanization state in a use state, so that spontaneous combustion is easily caused when the catalyst is in contact with air, the flame retardant can form a protective film on the surface of the catalyst to prevent the catalyst from being in contact with the air so as to prevent spontaneous combustion, and the flame retardant is not particularly limited, such as SHYZ-1 hydrogenation catalyst flame retardant.
Film-forming aid
When the flame retardant is used for the agent unloading of the hydrogenation device, the applicant finds that the closed cycle is required to be carried out for 12 hours at the temperature of 170 ℃, the surface of the catalyst is passivated, a layer of film with the thickness of about 10 microns is formed on the surface of the catalyst, and the film forming time is longer, so that in order to improve the efficiency, the quaternary ammonium salt is added as a film forming auxiliary agent, and a passivated film is quickly formed through the action of the quaternary ammonium salt and the flame retardant, the metal sulfide on the surface of the catalyst and the like, so that the closed cycle time is shortened.
In one embodiment, the film-forming assistant according to the present invention includes a quaternary ammonium salt, and the quaternary ammonium salt is at least one selected from alkyl quaternary ammonium salts, amido quaternary ammonium salts, and aryl quaternary ammonium salts, and the quaternary ammonium salt according to the present invention may be a chloride salt, a sulfate salt, a phosphate salt, and the like of the quaternary ammonium salt, and is not particularly limited.
Examples of the alkyl quaternary ammonium salt include, but are not limited to, tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tributylmethylammonium chloride, decyltrimethylammonium chloride, trimethyl-n-octylammonium chloride, lauryltrimethylammonium chloride, dodecyltrimethylammonium chloride, trimethyldodecylammonium chloride, trimethylmyristyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, trimethyltetradecylammonium chloride, tetrapropylammonium chloride, cetyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, trimethyloctadecylammonium chloride, tri-n-octylmethylammonium chloride, dilauryldimethylammonium chloride, tetrabutylammonium chloride, dimethyldioctadecylammonium chloride, dimethyldistearylammonium chloride.
Examples of amido quaternary ammonium salts include, but are not limited to, lauramidopropyltrimethylammonium methylsulfate, stearamidopropylethyldimethylammonium ethylsulfate, stearamidopropyltrimethylammonium methylsulfate, hydroxystearamidopropyltrimethylammonium methylsulfate, isononamidopropylethyldimethylammonium ethylsulfate, nonanamidopropylethyldimethylammonium ethylsulfate, methyl eicosanoic amidopropylethyldimethylammonium ethylsulfate.
Examples of the aryl quaternary ammonium salts include, but are not limited to, phenyltrimethylammonium chloride, benzyltrimethylammonium chloride, 1-dimethylpiperidinylphenylbenzyldimethylammonium chloride, phenyltriethylammonium chloride, benzyltriethylammonium chloride, benzyltributylammonium chloride.
Preferably, the quaternary ammonium salt is selected from at least one of C9-C20 alkyl quaternary ammonium salt and C9-C20 amido quaternary ammonium salt, more preferably at least one of C12-C20 alkyl quaternary ammonium salt and C12-C20 amido quaternary ammonium salt, and more preferably C12-C20 amido quaternary ammonium salt.
Cosolvent
Since the diesel oil or wax oil is generally used to replace the residual oil in the hydrogenation apparatus and then the flame retardant composition is injected to form a film during the unloading process, it is necessary to improve the dispersibility and compatibility in the diesel oil or wax oil, especially the nonpolar structure of the diesel oil, wax oil, etc., so that the quaternary ammonium salt is poorly compatible and dispersible. In one embodiment, the co-solvent of the present invention is selected from one or more of diesel oil, wax oil, petroleum acid, preferably petroleum acid.
Petroleum acid is a by-product obtained during the production and refining of light petroleum products in refineries, and during the processing of crude and synthetic oils. The catalyst meets the standard SH/T0530, mainly comprises naphthenic acid and other fatty acids, the boiling range of the catalyst is generally more than 220 ℃, and the catalyst can be classified into No. 85 petroleum acid (the acid value is more than 210mgKOH/g), No. 75 petroleum acid (the acid value is more than 200mgKOH/g and less than or equal to 210mgKOH/g), No. 65 petroleum acid (the acid value is more than 185mgKOH/g and less than or equal to 200mgKOH/g) and No. 55 petroleum acid (the acid value is more than 175mgKOH/g and less than or equal to 185mgKOH/g) according to the acid value.
Preferably, the acid value of the petroleum acid is 175-210 mgKOH/g, more preferably 185-210 mgKOH/g, and still more preferably 200-210 mgKOH/g.
The acid number represents the number of milligrams of potassium hydroxide (KOH) required to neutralize 1 gram of chemical, measured according to SH/T0092.
In one embodiment, the flame retardant composition of the present invention further comprises a penetration enhancer.
Permeation aid
In one embodiment, the permeation enhancer of the present invention is 1 to 5wt% of the flame retardant, which may be, for example, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%.
Preferably, the penetration enhancer of the present invention is selected from one or more of pyridinium, imidazolium and isoquinoline salts, preferably from pyridinium and imidazolium salts, and more preferably from imidazolium salts.
Examples of pyridinium salts include, but are not limited to, octylpyridinium chloride, decylpyridinium chloride, dodecylpyridinium chloride, tetradecylpyridinium chloride, hexadecylpyridinium chloride, octadecylpyridinium chloride, hexylpyridinium chloride.
Examples of the imidazole salt include, but are not limited to, 1-butyl-3-methylimidazolium salts such as 1-butyl-3-methylimidazolium bromide, 1-butyl-3-methylchloroimidazole, 1-butyl-3-methyltetrafluoroborate imidazole, 1-butyl-3-methylhexafluorophosphoric acid imidazole, 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt, 1-butyl-3-methyltetrachloroferrate imidazole, 1-butyl-3-methylimidazolium iodide, 1-butyl-3-methyltrifluoromethanesulfonate imidazole, 1-butyl-2, 3-dimethylimidazolium chloride, 1-butyl-3-methyltrifluoro (trifluoromethyl) borate imidazole, imidazole-N-oxide, and the like, 1-butyl-3-methyltributylimidazole, 1-butyl-3-methylthioimidazole; 1-butyl-2, 3-dimethylimidazolium salts, such as 1-butyl-2, 3-dimethylhexafluorophosphate imidazole, 1-butyl-2, 3-dimethyltetrafluoroborate imidazole, 1-butyl-2, 3-dimethylimidazolium bis (trifluoromethanesulfonyl) imide salt, 1-butyl-2, 3-dimethyltrifluoromethanesulfonate imidazole; 1, 3-dialkyldimethylimidazolium salts, such as 1, 3-dimethyldimethylimidazole phosphate, 1, 3-dimethylimidazole chloride; 1, 3-bis (1-adamantyl) tetrafluoroboric acid imidazole, 1, 3-diisopropyltetrafluoroboric acid imidazole, 1, 3-di-tert-butyltetrafluoroboric acid imidazole; 1, 3-diarylimidazolium salts, such as 1, 3-bis (2,4, 6-trimethylphenyl) imidazolium chloride, 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride; 1, 3-dicycloalkylimidazolium salts, such as 1, 3-dicyclohexyltetrafluoroboric acid imidazole, 1, 3-dicyclohexylimidazolium chloride; 1, 2-dimethyl-3-propyl imidazole iodide; 1-ethyl-3-methylimidazolium salts, such as 1-ethyl-3-methyltrifluoro (trifluoromethyl) boronic acid imidazole, 1-ethyl-3-methylacetic acid imidazole; 1-hexyl-3-methylimidazolium salts, such as 1-hexyl-3-methylimidazolium chloride, 1-hexyl-3-methylhexafluorophosphate, 1-hexyl-3-methyltetrafluoroborate imidazole, 1-hexyl-3-methyltrifluoromethanesulfonate imidazole, 1-hexyl-3-methylbromide imidazole, 1-hexyl-2, 3-dimethyliodide imidazole, 1-hexyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt; 1-methyl-3-alkylimidazolium salts, for example 1-methyl-3-propylimidazolium iodide, 1-methyl-3-n-octylimidazolium bromide, 1-methyl-3-n-octylimidazolium chloride, 1-methyl-3-n-octylimidazolium hexafluorophosphate, 1-methyl-3- [6- (methylsulfinyl) hexyl ] p-toluenesulfonate, 1-methyl-3-n-octyltrifluoromethanesulfonic acid, 1-methyl-3-n-octyltetrafluoroboric acid imidazolium. The imidazolium salt can be imidazole chloride salt, iodide salt, tetrafluoroborate, tetrachloroferrate, trifluoro (trifluoromethyl) borate, trifluoromethanesulfonimide salt, trifluoromethanesulfonate and the like, and the anion of the imidazolium salt is not particularly limited.
As examples of isoquinoline salts, include, but are not limited to, chloroisoquinoline salts.
By adding short-chain alkyl substituted pyridinium or imidazolium salt and the like, when the catalyst is aggregated together, a flame retardant, a film-forming auxiliary agent, a cosolvent and the like can be driven to enter the catalyst, the condition that a local catalyst is unstable after film forming is avoided, the temperature of the catalyst is reduced in reddish brown after the catalyst is removed, or the temperature is rapidly increased under the condition of air illumination, and the applicant finds that when the micromolecule imidazolium salt containing two nitrogen atoms, especially the imidazolium salt with different carbon chain lengths is used, the catalyst is more favorable for being permeated with other components of the composition together, a more uniform and compact passivation film is formed, and the stability of the catalyst is promoted. More preferably, the permeation enhancer of the present invention comprises at least one N-alkyl functional group. Further preferably, the N-alkyl functional group of the present invention is an N-C1-C6 alkyl functional group. More preferably, the pyridinium of the present invention is 1-C1-C6 alkylpyridinium, the imidazolium is 1- (C1-C6 alkyl) -3- (C1-C6 alkyl) imidazolium and its derivatives, and the derivatives of the 1-alkyl-3-alkylimidazolium are derivatives obtained by substituting a hydrogen atom on an imidazole heterocycle of 1-alkyl-3-alkylimidazolium with an alkyl group, such as methyl, ethyl, propyl, and the like, and are not particularly limited. In a preferred embodiment, the imidazole salt of the present invention is 1- (C4-C6 alkyl) -3- (C1-C3 alkyl) imidazole salt and/or 1- (C1-C3 alkyl) -3- (C4-C6 alkyl) imidazole salt and derivatives thereof.
In one embodiment, the coalescent of the present invention further comprises a glycol fatty acid ester.
Ethylene glycol fatty acid ester
In one embodiment, the glycol fatty acid ester of the present invention is a glycol mono-fatty acid ester and/or a glycol di-fatty acid ester.
Examples of ethylene glycol mono fatty acid esters include, but are not limited to, ethylene glycol monooleate, ethylene glycol monopalmitate (ethylene glycol monopalmitate), ethylene glycol monostearate (ethylene glycol monostearate), ethylene glycol monooleate, ethylene glycol linolenate, ethylene glycol monooleate, ethylene glycol arachidonate, ethylene glycol monopalmitate.
Examples of glycol di-fatty acid esters include, but are not limited to, ethylene glycol dipalmitate (ethylene glycol dipalmitate), ethylene glycol dioctadecylate, ethylene glycol dilinoleate, ethylene glycol arachidonate, ethylene glycol distearate, ethylene glycol dipalmitate, ethylene glycol dilaurate.
Because of the penetration of the permeation promoter and the compatibility of the cosolvent with diesel oil and wax oil, the oil content on the surface of the catalyst is higher in the gas cooling and purging process, especially the initial temperature of the gas cooling process is lower, so that the oil covered by the catalyst is more difficult to separate, which also influences the activity after regeneration. Preferably, the ethylene glycol mono-fatty acid ester is ethylene glycol mono-C10-C20 fatty acid ester, more preferably ethylene glycol mono-C12-C20 fatty acid ester. More preferably, the weight ratio of the glycol fatty acid ester to the quaternary ammonium salt is 1: (3 to 7), there may be mentioned, 1: 3. 1: 4. 1: 5. 1: 6. 1: 7.
in a second aspect, the present invention provides a method for using the flame retardant composition for hydrogenation catalysis, which comprises:
(1) cooling and reducing the volume;
(2) wax oil displacement;
(3) diesel oil displacement;
(4) injecting a flame retardant composition;
(5) forming a film;
(6) and (5) cooling and replacing the gas.
In one embodiment, the method of using the flame retardant composition for hydrogenation catalysis of the present invention comprises:
(1) cooling and reducing the volume: the reactor bed temperature is first reduced from the operating temperature to 350 ℃ at a rate of 15-20 ℃ per hour;
(2) wax oil displacement: when the temperature of the reactor is reduced to 350 ℃, introducing wax oil from a start-up straight-run wax oil pipeline at a speed of 50t/h, replacing residual oil in a reaction system, gradually increasing the amount of the wax oil to the maximum amount of a pump of 200t/h after stabilization, and correspondingly reducing the input amount of the residual oil to zero; the reaction system is circulated for 18 hours at 320 ℃; after wax oil displacement is qualified, the temperature of the reactor is continuously reduced to 290 ℃ at the cooling speed of 15-20 ℃/h, and the pressure of a reaction system is reduced to 12.0Mpa at the rate of 1-1.5Mpa/h per hour;
(3) diesel oil replacement: introducing a diesel oil displacement reaction system at a speed of 50t/h, gradually increasing the diesel oil feeding amount to the maximum amount of a pump of 200t/h, and circulating; meanwhile, the reaction temperature is continuously reduced to 200 ℃ at the speed of 5 ℃/h, and the diesel oil is replaced for about 9 hours;
(4) injection of flame retardant composition: when the temperature dropped below 200 ℃ and the displacement was acceptable (viscosity less than 12Cst at 50 ℃), the flame-retardant composition was injected from the reaction feed pump inlet line and the time required for the oil displacement (wax oil and diesel) was about 30 hours. The oil is a mixture of wax oil and diesel oil, and the proportion of the wax oil to the diesel oil is 1: (10-100), in the process of injecting the agent, cooling the bed layer temperature of the reactor from 200 ℃ to about 170 ℃;
(5) film forming: after the flame-retardant composition is added, the temperature of a reaction system is kept at 170 ℃ for closed cycle for 6-12 hours, and the surface of the catalyst is passivated to form a layer of film with the diameter of about 10 micrometers on the surface of the catalyst;
(6) gas cooling and replacement: after the oil circulation cooling is stopped, the gas circulation cooling is continued, and meanwhile, the oil in the catalyst, the pipeline and the device is purged; when the temperature of the reactor bed layer is reduced to below 50 ℃, the operation of the circulating gas compressor is stopped.
The method of using the flame retardant composition for hydrogenation catalysis is not specifically limited in the present invention, and reference is made to the method of using CN 109135810A.
Examples
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
A1: flame retardant
The flame retardant is a SHYZ-1 hydrogenation catalyst flame retardant.
B1: film-forming aid
The film-forming aid is stearamidopropyl trimethyl ammonium methyl sulfate.
B2: film forming aid
The film-forming aid is lauramide propyl trimethyl ammonium methyl sulfate.
B3: film-forming aid
The film-forming assistant is behenyl trimethyl ammonium methyl sulfate.
B4: film forming aid
The film-forming assistant is trimethyl octadecyl ammonium chloride.
B5: film forming aid
The film-forming assistant is ethylene glycol monopalmitate.
B6: film-forming aid
The film-forming additive is ethylene glycol mono-octadecenoic acid ester.
B7: film forming aid
The film-forming assistant is ethylene glycol dipalmitate.
C1: cosolvent
The cosolvent is No. 75 petroleum acid.
C2: cosolvent
The cosolvent is No. 65 petroleum acid.
C3: cosolvent
The cosolvent is No. 55 petroleum acid.
C4: cosolvent
The cosolvent is diesel oil.
D1: penetration aid
The penetration enhancer is 1-butyl-3-methyltetrafluoroborate imidazole.
D2: permeation aid
The penetration enhancer is 1-butyl-2, 3-dimethyl imidazole chloride.
D3: penetration aid
The penetration enhancer is 1-hexyl-3-methyl trifluoro methane sulfonic acid imidazole.
D4: permeation aid
The penetration enhancer is 1, 3-dimethyl imidazole chloride.
D5: permeation aid
The penetration enhancer is hexylpyridinium chloride.
TABLE 1
Examples 1-11 provide a flame retardant composition, which is prepared from the raw materials in parts by weight shown in table 1.
Embodiments 1 to 11 also provide a method for preparing the flame retardant composition, which includes mixing the raw materials for preparing the flame retardant composition to obtain the flame retardant composition.
Evaluation of Performance
The flame-retardant composition provided by the embodiment is subjected to catalyst unloading, and the specific using method comprises the following steps:
(1) cooling and reducing the volume: the reactor bed temperature is first reduced from the operating temperature to 350 ℃ at a rate of 15-20 ℃ per hour;
(2) wax oil displacement: when the temperature of the reactor is reduced to 350 ℃, introducing wax oil from a start-up straight-run wax oil pipeline at a speed of 50t/h, replacing residual oil in a reaction system, gradually increasing the amount of the wax oil to the maximum amount of a pump of 200t/h after stabilization, and correspondingly reducing the input amount of the residual oil to zero; the reaction system is circulated for 18 hours at 320 ℃; after wax oil displacement is qualified, the temperature of the reactor is continuously reduced to 290 ℃ at the cooling speed of 15-20 ℃/h, and the pressure of a reaction system is reduced to 12.0Mpa at the rate of 1-1.5Mpa/h per hour;
(3) diesel oil replacement: introducing a diesel oil displacement reaction system at a speed of 50t/h, gradually increasing the diesel oil feeding amount to the maximum amount of a pump of 200t/h, and circulating; meanwhile, the reaction temperature is continuously reduced to 200 ℃ at the speed of 5 ℃/h, and the diesel oil is replaced for about 9 hours;
(4) injection of flame retardant composition: when the temperature drops below 200 ℃ and the substitution is acceptable (viscosity at 50 ℃ C. is less than 12Cst), the flame-retardant composition is injected from the reaction feed pump inlet line, the time required for the substitution of the oils (wax oil and diesel) is about 30 hours, the composition is 3% by weight of the oil, the oil is a mixture of wax oil and diesel, and the ratio of the oil to the diesel is 1: 50, in the process of injecting the agent, reducing the temperature of a reactor bed layer from 200 ℃ to about 170 ℃;
(5) film forming: after the flame-retardant composition is added, the temperature of a reaction system is kept at 170 ℃ for closed cycle for 8 hours, and the surface of the catalyst is passivated to form a layer of film with the diameter of about 10 micrometers on the surface of the catalyst;
(6) gas cooling and replacement: after the oil circulation cooling is stopped, the gas circulation cooling is continued, and meanwhile, the oil in the catalyst, the pipeline and the device is purged; when the temperature of the reactor bed layer is reduced to below 50 ℃, the operation of the circulating gas compressor is stopped.
1. And (3) testing the flame retardant property: after the catalyst treated by the unloading agent is wiped by using filter paper, the catalyst and the filter paper are put into an infrared oven for heating, the temperature of reddish brown and the temperature of beginning to smoke are observed, and the temperature is graded, wherein the temperature of grade 1 is not more than 120 ℃, the temperature of grade 2 is more than 120 ℃, not more than 140 ℃, the temperature of grade 3 is more than 140 ℃, not more than 160 ℃, the temperature of grade 4 is more than 160 ℃, not more than 180 ℃, the temperature of grade 5 is more than 180 ℃, not more than 200 ℃, the temperature of grade 6 is more than 200 ℃, not more than 220 ℃, the temperature of grade 7 is more than 220 ℃, not more than 240 ℃ and the temperature of grade 8 is more than 240 ℃, and the results are shown in Table 2.
Table 2 characterization test of properties
2. Environmental stability: the catalyst before agent removal and the catalyst after agent removal were placed under light, air and 37 ℃ for 6 hours, respectively, the temperature T0 increased in the middle of the catalyst before agent removal and the temperature T1 increased in the middle of the catalyst after agent removal were measured with a thermometer, respectively, and the difference T0-T1 in the temperature increases before and after agent removal was calculated and evaluated, wherein the difference in temperature increases was greater than 10 ℃ in the 1-stage, less than or equal to 10 ℃ in the 2-stage, less than or equal to 8 ℃ in the 3-stage, less than or equal to 8 ℃ in the 6-stage, and less than or equal to 6 ℃ in the 4-stage, and the results are shown in table 3.
Table 3 performance characterization test
| Examples | Environmental stability |
| 1 | Grade 3 |
| 2 | Level 1 |
| 3 | Level 1 |
| 4 | Level 1 |
| 5 | Level 1 |
| 6 | 4 stage |
| 9 | Stage 2 |
| 10 | Stage 2 |
3. Oil content: the catalyst treated by the above-mentioned stripping agent is extracted with benzene-ethanol, the change rate of carbon content in the catalyst before and after extraction is calculated as oil content, wherein the oil content is (carbon content of catalyst before extraction-carbon content of catalyst after extraction)/carbon content of catalyst before extraction is 100%, the oil content is evaluated, the oil content is 1 grade, the oil content is less than or equal to 2%, the oil content is 2 grade, the oil content is less than or equal to 4%, the oil content is 3 grade, the oil content is less than or equal to 5%, the oil content is 4 grade, the oil content is more than 5% and less than or equal to 7% in 4 grade, the oil content is more than 7% in 5 grade, and the results are shown in table 4.
Table 4 characterization test of properties
The test results in tables 2 to 4 show that the flame retardant composition for hydrogenation catalysis provided by the invention can be used for an agent unloading agent of a hydrogenation catalyst, can quickly form a uniform passive film, can improve the flame retardant performance, does not influence the regeneration activity of the catalyst, and can be used for industrial treatment.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Where the claims recite a range of values, such ranges are intended to include all sub-ranges subsumed therein, and variations within the ranges are intended to be encompassed by the claims as appended hereto where possible.
Claims (4)
1. The flame-retardant composition for hydrogenation catalysis is characterized by comprising 100 parts of flame retardant, 5-15 parts of film-forming assistant and 5-10 parts of cosolvent by weight,
the cosolvent consists of diesel oil, wax oil and petroleum acid,
the acid value of the petroleum acid is 175-210 mgKOH/g,
the preparation raw materials of the flame-retardant composition also comprise a penetration enhancer, the penetration enhancer is selected from one or more of pyridinium, imidazolium and isoquinoline salts, the penetration enhancer comprises at least one N-alkyl functional group,
the N-alkyl functional group is an N-C1-C6 alkyl functional group,
the film-forming aid comprises quaternary ammonium salt, and the quaternary ammonium salt is at least one of alkyl quaternary ammonium salt, amido quaternary ammonium salt and aryl quaternary ammonium salt.
2. The flame retardant composition for hydrogenation catalysis according to claim 1, wherein the quaternary ammonium salt is at least one selected from the group consisting of C9-C20 alkyl quaternary ammonium salts and C9-C20 amido quaternary ammonium salts.
3. The flame retardant composition for hydrogenation catalysis according to claim 1, wherein the permeation promoter accounts for 1 to 5wt% of the flame retardant.
4. A method for using the flame retardant composition for hydrogenation catalysis according to any one of claims 1 to 3, characterized by comprising:
(1) cooling and reducing the volume;
(2) wax oil displacement;
(3) diesel oil displacement;
(4) injecting a flame retardant composition;
(5) forming a film;
(6) and (5) cooling and replacing the gas.
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| US4724064A (en) * | 1983-11-17 | 1988-02-09 | Betz Laboratories, Inc. | Composition and method for coke retardant during hydrocarbon processing |
| CN1140613C (en) * | 2002-04-12 | 2004-03-03 | 江苏天鹏石化特种工程有限公司 | Process for unloading catalyst from petrochemical equipment |
| CN102343287B (en) * | 2010-07-29 | 2014-05-28 | 中国石油化工股份有限公司 | Oily dispersion medium for solid powder catalyst, preparation method and application thereof |
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| CN106497597B (en) * | 2016-10-18 | 2018-08-21 | 华东理工大学 | A method of carrying out high-acid crude oil depickling using phase transfer catalyst |
| CN109135810A (en) * | 2018-10-25 | 2019-01-04 | 上海阳申石化设备安装有限公司 | A kind of application method of SHYZ-1 hydrogenation catalyst fire retardant |
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