CN108435262A - Olefine aldehydr vapor phase method synthesizes the processing method for the carbon deposition catalyst that isoprene generates - Google Patents
Olefine aldehydr vapor phase method synthesizes the processing method for the carbon deposition catalyst that isoprene generates Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
- B01J38/58—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids and gas addition thereto
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen
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- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
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- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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Abstract
The present invention provides a kind of processing methods of carbon deposition catalyst, include the following steps, first under conditions of hydrogen, after carbon deposition catalyst, catalyst and organic solvent are reacted, reaction system is obtained, then after being washed to reaction system, obtains solidliquid mixture；Then after the solidliquid mixture that above-mentioned steps obtain being detached, solid and organic solution are obtained；After finally the solid that above-mentioned steps obtain is roasted, the regenerated catalyst that obtains that treated.The present invention can not only effectively reduce the discharge of a large amount of hydrocarbons generated in carbon deposition catalyst roasting process, greatly reduce the pollution to environment, reduce cumbersome subsequent treatment process and processing cost, and the organic liquid separated, it can also be handled by fractionation, obtain fuel oil, realize the closed loop process for comprehensive utilization of turning waste into wealth, it is environment friendliness, meet the sustainable development idea of environment-friendly and green.
Description
Technical field
The present invention relates to olefine aldehydr vapor phase methods to synthesize isoprene technical field, is related to a kind of processing side of carbon deposition catalyst
The processing method for the carbon deposition catalyst that method more particularly to olefine aldehydr vapor phase method synthesis isoprene generate.
Background technology
Isoprene is the essential raw material of natural man-made rubber, especially in terms of synthesizing specific rubber product
Using being that other industrial chemicals are irreplaceable.Currently, the main method for preparing isoprene is divided into physical partition method and chemistry
Synthetic method.Physical partition method is to extract its C5 fraction by naphtha pyrolysis ethylene, and this method is limited by market fluctuation
System, and against the continuous development of rubber industry, increasingly increase severely to high-performance natural man-made rubber demand, this is to traditional physics
Divide and propose huge challenge, thus develops chemical synthesis synthesis isoprene and provide new approaches to solve this problem.Change
Method includes mainly isobutene-formaldehyde method, acetylene acetone method and propylene dimerization, wherein C4 resources are utilized, with isobutene and first
Aldehyde as raw material gas-phase one-step method is simple for process, investment is small, cost of material is relatively low advantage, there is considerable economic effect
Benefit.The technology is formaldehyde and isobutene mixing gasifying to be passed through reactor, in the effect of catalyst under 150~400 DEG C of normal pressures
Lower dehydrating condensation prepares isoprene, and this method has the characteristics that flow is short, product is easily separated, easy to operate, investment is small,
It receives significant attention in the industry.
Currently, catalyst involved during isobutene and formaldehyde gas-phase one-step method synthesis isoprene mainly has phosphorus system
Catalyst, Cu-series catalyst, molecular sieve catalyst, silver-colored series catalysts etc., the RU2354450C1 as disclosed in Russ P,
RU2421441C1, CN201610161038.6 disclosed in Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences,
CN201610944377.1.But these catalyst all have the characteristics that solid acid, thus during the reaction would generally be serious
Carbon distribution causes to inactivate, and then affects being normally carried out for reaction.
Conventional carbon deposition catalyst regeneration and treatment technique in field, mainly by under air conditions high-temperature roasting remove
Carbon distribution recharges the recycling for realizing catalyst.But heating rate cannot be too fast in roasting for this method, otherwise can
Lead to catalyst activity component migration, sintering etc., destroys catalyst activity, and carbon distribution cannot be fully converted into carbon dioxide；
But even if reducing heating rate, it can not completely convert carbon distribution to carbon dioxide or carbon monoxide, also result in product
Light component in carbon is volatilized first, and heavy constituent can also decompose at high temperature, while generating small molecule hydrocarbon, can be with nitrogen oxygen
The photochemical reaction of compound generates strong oxidizer, and serious harm is generated to human body and plant, so affect subsequent processing and
The difficulty utilized.
Therefore, how carbon deposition catalyst is handled, reduces the discharge of hydrocarbon in its roasting process, and can utilize rationally
Utilize carbon distribution, it has also become many forward-looking researchers widely one of focus of attention in the industry.
Invention content
In view of this, the technical problem to be solved in the present invention is to provide a kind of processing method of carbon deposition catalyst, especially
It is a kind of processing method of the carbon deposition catalyst generated for olefine aldehydr vapor phase method synthesis isoprene, processing side provided by the invention
Method can effectively reduce the discharge of a large amount of hydrocarbons generated in carbon deposition catalyst roasting process, greatly reduce pair
The pollution of environment, and mild condition is quick, simple process and low cost, is conducive to industrialized production and popularization and application.
The present invention provides a kind of processing methods of carbon deposition catalyst, include the following steps：
1) under conditions of hydrogen, after carbon deposition catalyst, catalyst and organic solvent are reacted, reactant is obtained
System, then after being washed to reaction system, obtain solidliquid mixture；
2) after being detached the solidliquid mixture that above-mentioned steps obtain, solid and organic solution are obtained；
3) after the solid that above-mentioned steps obtain being roasted, the regenerated catalyst that obtains that treated.
Preferably, the catalyst is metallic catalyst；
The metal includes one or more in Ru, Pd, Pt, Co, Ni and Ir；
The carbon deposition catalyst is the carbon deposition catalyst that olefine aldehydr vapor phase method synthesizes that isoprene generates.
Preferably, the catalyst is loaded catalyst；
The load capacity is 0.1%~5%；
The carrier is acid carrier.
Preferably, the organic solvent include toluene, paraxylene, ortho-xylene, phenol, hydroquinone, benzyl alcohol and
It is one or more in hexamethylene；
The acid carrier include SBA-15, ZSM-5, X-type molecular sieve, Y type molecular sieve, beta-molecular sieve, SAPO molecular sieve,
Al/SiO2、Al2O3、Zr/SiO2And ZrO2In it is one or more.
Preferably, the mass ratio of the catalyst and carbon deposition catalyst is 1：(10~30)；
The pressure of the hydrogen is 2.0~4.0MPa；
The volume ratio of the carbon deposition catalyst and organic solvent is 1：(1.8~2.5).
Preferably, the step 1) can carry out 1 time, or repeat 1~3 time；
The temperature of the reaction is 130~200 DEG C；
The time of the reaction is 1.5~5h.
Preferably, the temperature of the roasting is 450~600 DEG C；
The time of the roasting is 3~10h.
Preferably, further include drying steps before the roasting；
The temperature of the drying is 60~80 DEG C；
The time of the drying is 3~10h.
Preferably, after the organic solution is fractionated into, fuel oil is obtained.
Preferably, the fraction of the fractionation includes 60~180 DEG C of light Fuel oil ingredient and/or 180 DEG C or more of weight
Matter fuel oil ingredient.
The present invention provides a kind of processing methods of carbon deposition catalyst, include the following steps, first under conditions of hydrogen,
After carbon deposition catalyst, catalyst and organic solvent are reacted, reaction system is obtained, then after being washed to reaction system,
Obtain solidliquid mixture；Then after the solidliquid mixture that above-mentioned steps obtain being detached, solid and organic solution are obtained；Most
After the solid that above-mentioned steps obtain is roasted afterwards, the regenerated catalyst that obtains that treated.Compared with prior art, of the invention
For in the regeneration process of existing carbon deposition catalyst routine, direct high-temperature roasting removes carbon distribution, can there is catalyst work
Property component migration, sintering, destroy catalyst activity, but also will produce hydrocarbon and a variety of lack such as pollute the environment
It falls into.The especially carbon deposition catalyst of olefine aldehydr vapor phase method synthesis isoprene, roasting direct processing can cause a large amount of low boiling points hydrocarbon
Compound (including aromatic compound) volatilization is discharged into air, strong oxidizer is generated with the photochemical reaction of oxynitrides, to people
Body and plant generate serious harm.
The present invention is conducted in-depth research and is explored in the complicated composition to carbon deposition catalyst, especially olefine aldehydr vapor phase method
The carbon deposition catalyst of isoprene is synthesized, composition is especially complicated, aromatic hydrocarbons, the saturation/unsaturated acyclic hydrocarbon of predominantly 7~12 carbon
Class, aliphatic or aromatic ester, acid, ether and alcohols, also coke etc..A kind of carbon distribution of proposing of the invention is urged
The carbon deposition catalyst of olefine aldehydr reaction is carried out hydrogenation deoxidation, then washes extraction and separation by the processing method of agent, to eliminate
The organic principle of the overwhelming majority, finally carries out roasting activity recovery again；Carbon deposition catalyst can not only effectively be reduced to roast
The discharge of a large amount of hydrocarbons generated in journey greatly reduces the pollution to environment, reduces cumbersome subsequent processing work
Skill and processing cost, and the organic liquid separated, additionally it is possible to handled by fractionation, obtain fuel oil, realize become give up into
The closed loop process of treasured comprehensive utilization, it is environment friendliness, meet the sustainable development idea of environment-friendly and green.Meanwhile the present invention carries
The processing method of confession, mild condition is quick, simple process and low cost, is conducive to industrialized production and popularization and application.
The experimental results showed that carbon deposition catalyst, in a solvent after hydrogenation reaction, carbon distribution content significantly reduces, after dry
Catalyst roasted, realize the regeneration of catalyst；And the organic solution obtained after hydrogenated reaction is alkanes.
Description of the drawings
Fig. 1 is the gas-chromatography-for the carbon deposition catalyst that olefine aldehydr vapor phase method provided by the invention synthesizes during isoprene
Mass spectrum GC-MS analyzes collection of illustrative plates；
Fig. 2 is the fractionating device simplified schematic diagram of two-part provided by the invention fractionation.
Specific implementation mode
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are intended merely to the feature and advantage further illustrated the present invention, rather than to invention claim
Limitation.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to people in the art
It is prepared by conventional method known to member.
All raw materials of the present invention, are not particularly limited its purity, and present invention preferably employs analyze pure or molecular sieve catalytic
The purity requirement of agent preparation field routine.
All raw materials of the present invention, the trade mark and abbreviation belong to this field routine trade mark and abbreviation, each trade mark and abbreviation
In the field of its associated uses be it is explicit, those skilled in the art according to the trade mark, abbreviation and corresponding purposes,
It can be commercially available from city's mid-sales or conventional method is prepared.
The present invention provides a kind of processing methods of carbon deposition catalyst, include the following steps：
1) under conditions of hydrogen, after carbon deposition catalyst, catalyst and organic solvent are reacted, reactant is obtained
System, then after being washed to reaction system, obtain solidliquid mixture；
2) after being detached the solidliquid mixture that above-mentioned steps obtain, solid and organic solution are obtained；
3) after the solid that above-mentioned steps obtain being roasted, the regenerated catalyst that obtains that treated.
The present invention under conditions of hydrogen, after carbon deposition catalyst, catalyst and organic solvent are reacted, obtains first
Reaction system, then after being washed to reaction system, obtain solidliquid mixture.
The catalyst activity component and form is not particularly limited in the present invention, with it is well known to those skilled in the art this
The component and form of the catalyst of class routine, those skilled in the art can according to practical condition, product requirement with
And quality requirement is selected and is adjusted, catalyst of the present invention is preferably metallic catalyst, more preferably supported catalyst
Agent, most preferably loaded catalyst.
The specific ingredient of the catalyst and parameter is not particularly limited in the present invention, with it is well known to those skilled in the art this
The conventional ingredient and parameter of class catalyst, those skilled in the art can according to practical condition, product requirement and
Quality requirement is selected and is adjusted, and the active component of catalyst of the present invention preferably includes in Ru, Pd, Pt, Co, Ni and Ir
One or more, more preferably Ru, Pd, Pt, Co, Ni or Ir.The carrier of catalyst of the present invention is preferably acid carrier,
More specifically it is preferably SBA-15, ZSM-5, X-type molecular sieve, Y type molecular sieve, beta-molecular sieve, SAPO molecular sieve, Al/SiO2、Al2O3、
Zr/SiO2And ZrO2In it is one or more, more preferably SBA-15, ZSM-5, X-type molecular sieve, Y type molecular sieve, beta-molecular sieve,
SAPO molecular sieve, Al/SiO2、Al2O3、Zr/SiO2Or ZrO2, more preferably SBA-15, ZSM-5, SAPO molecular sieve, Al/SiO2
Or Zr/SiO2.Load capacity of the present invention is preferably 0.1%~5%, more preferably 0.5%~4.5%, more preferably 1%~
4%, more preferably 2%~3%, are specifically as follows 0.5%~3.0%.
The dosage of the catalyst is not particularly limited in the present invention, is urged so that routine well known to those skilled in the art is such
The conventional amount used of agent, those skilled in the art can according to the actual application, product requirement and quality requirement into
Row selection and adjustment, the present invention is to be further ensured that the reduction effect of product, the mass ratio of the catalyst and carbon deposition catalyst
Preferably 1：(10~30), more preferably 1：(13~27), more preferably 1：(15~25), more preferably 1：(17~23).
The carbon deposition catalyst is not particularly limited in the present invention, is existed with conventional catalyst well known to those skilled in the art
During use, will produce carbon distribution situation, those skilled in the art can according to practical condition, product requirement with
And quality requirement is selected and is adjusted, carbon deposition catalyst of the present invention preferably refers in catalytic reaction process, due to product
The case where carbon causes catalyst inactivation or activity to decline, clogged with soot duct on catalyst and clad surface.Institute of the present invention
It states carbon deposition catalyst and is more preferably the carbon deposition catalyst generated during catalyst olefine aldehydr vapor phase method synthesis isoprene.
The specific type and parameter of the carbon deposition catalyst is not particularly limited in the present invention, ripe with those skilled in the art
The type and parameter for the conventional carbon deposition catalyst known, those skilled in the art can want according to practical situations, product
It asks and quality requirement is selected and adjusted, carbon deposition catalyst of the present invention preferably includes phosphorus series catalysts, copper system catalysis
One or more in agent, molecular sieve catalyst and silver-colored series catalysts, the active component of the carbon deposition catalyst may be member
It is one or more in the compound of plain Cr, Mo, W, P and above-mentioned element.The carrier of carbon deposition catalyst of the present invention is preferably
SiO2, more preferably SiO2Microballoon.The load capacity of carbon deposition catalyst of the present invention is preferably 0.1%~30%, more preferably
1%~25%, more preferably 5%~20%, more preferably 10%~15%, are specifically as follows 15%~25%.Institute of the present invention
The grain size for stating carbon deposition catalyst is preferably 50~500 μm, more preferably 100~400 μm, more preferably 200~300 μm.
The specific choice of the organic solvent is not particularly limited in the present invention, with routine well known to those skilled in the art
Organic solvent, those skilled in the art can select according to practical condition, product requirement and quality requirement
And adjustment, organic solvent of the present invention preferably include toluene, paraxylene, ortho-xylene, phenol, hydroquinone, benzyl alcohol
With it is one or more in hexamethylene, more preferably toluene, paraxylene, ortho-xylene, phenol, hydroquinone, benzyl alcohol or
Hexamethylene, more preferably toluene, paraxylene, phenol, benzyl alcohol or hexamethylene.
The dosage of the organic solvent is not particularly limited in the present invention, with well known to those skilled in the art such organic
The conventional amount used of solvent, those skilled in the art can according to needs of production, product requirement and quality requirement into
Row selection and adjustment, the present invention are to ensure the reduction effect of product, ensure that reaction carries out in liquid-phase system, the organic solvent
Preferably meet the quantity of solvent needed for infusion process, the volume ratio of the specific carbon deposition catalyst and organic solvent is preferably 1：
(1.8~2.5), more preferably 1：(1.9~2.4), more preferably 1：(2.0~2.3).
The intake of the hydrogen is not particularly limited in the present invention, with well known to those skilled in the art such organic molten
The conventional amount used of agent, those skilled in the art can carry out according to needs of production, product requirement and quality requirement
Selection and adjustment, hydrogen of the present invention can be disposably to be passed through pressurize before reacting, or be continually fed into during the reaction.This
The pressure for inventing the hydrogen is preferably the pressure before reacting, and the pressure occurrence of the hydrogen is preferably 2.0~4.0MPa, more
Preferably 2.2~3.8MPa, more preferably 2.5~3.5MPa, more preferably 2.7~3.3MPa, it is specifically as follows 2.5~
3.5MPa。
The condition of the reaction is not particularly limited in the present invention, with the normal of such reaction well known to those skilled in the art
Rule condition, those skilled in the art can be selected according to needs of production, product requirement and quality requirement and
Adjustment, the temperature of reaction of the present invention is preferably 130~200 DEG C, more preferably 140~190 DEG C, more preferably 150~180
DEG C, more preferably 160~170 DEG C, it is specifically as follows 140~170 DEG C.The time of reaction of the present invention is preferably 1.5~5h,
More preferably 2~4.5h, more preferably 2.5~4h, more preferably 3~3.5h, are specifically as follows 2~4h.
The present invention obtains reaction system after above-mentioned liquid phase method reduction reaction, then after being washed to reaction system, obtains
To solidliquid mixture.
Washing of the present invention refers to being washed to whole system, including the solid phase in reaction system and liquid phase.This hair
The bright washing preferably refers to washing extraction.The present invention is the effect for improving washing and removing the impurity such as acid, alcohol, the washing
Water is preferably distilled water and/or deionized water, more preferably distilled water.
The carry out number of above-mentioned reaction and washing is not particularly limited in the present invention, and those skilled in the art can be according to reality
Border production needs, product requirement and quality requirement are selected and adjusted, and the present invention is to improve the processing effect of carbon deposition catalyst
Fruit further decreases the yield of hydrocarbon in roasting process, and the step 1) can carry out 1 time, or repeat 1~
3 times；It more preferably carries out 1 time, or repeats 1~2 time.
The present invention is that complete and micronization processes process, above-mentioned steps are specifically as follows：
Carbon deposition catalyst is placed in autoclave, is passed through hydrogen, under certain reaction condition, by liquid phase method, to have
Solvent is reaction medium, and hydrogenation deoxidation reaction is carried out under the catalyst actions such as Ru, Pd, Pt, Co, Ni or Ir.It again will be above-mentioned
System obtained by step is through washing deacidification, alcohol etc..It repeats the above steps 1~2 time.
Then the present invention detaches the solidliquid mixture that above-mentioned steps obtain after, solid and organic solution are obtained.
The mode, process and parameter of the separation is not particularly limited in the present invention, with well known to those skilled in the art
Mode, process and the parameter routinely detached, those skilled in the art can according to needs of production, product requirement and
Quality requirement is selected and is adjusted, and separation of the present invention is preferably separated by solid-liquid separation.Separation of the present invention further includes that will accumulate
C catalyst and catalyst are detached, and above-mentioned separation can carry out screening separation by the difference of grain size.
After the present invention finally roasts the solid that above-mentioned steps obtain, the regenerated catalyst that obtains that treated.
The condition of the roasting is not particularly limited in the present invention, with the normal of such reaction well known to those skilled in the art
Roasting condition is advised, those skilled in the art can select according to needs of production, product requirement and quality requirement
It selects and adjusts, the temperature of roasting of the present invention is preferably 450~600 DEG C, more preferably 475~575 DEG C, more preferably 500
~550 DEG C.The time of the roasting is preferably 3~10h, more preferably 4~9h, more preferably 6~7h, it is specifically as follows 5~
8h。
The present invention is to ensure the treatment effect of carbon deposition catalyst, the complete and entire processing step of refinement, excellent before the roasting
Choosing further includes drying steps.The mode of drying of the present invention is preferably dried in vacuo.The temperature of drying of the present invention is preferred
It is 60~80 DEG C, more preferably 63~78 DEG C, more preferably 65~75 DEG C.The time of drying of the present invention is preferably 3~
10h, more preferably 4~9h, more preferably 6~7h, are specifically as follows 4~6h.
The present invention is that complete and micronization processes process, above-mentioned steps are specifically as follows：
By solidliquid mixture separating catalyst and organic solution, catalyst is further dried in vacuo, and cycle is used for after roasting
Reaction.
The processing mode of the organic solution is not particularly limited in the present invention, and those skilled in the art can be according to reality
Production needs, processing requirement and quality requirement are selected and adjusted, and the present invention is the entire processing of further complete and refinement
Step achievees the purpose that comprehensively utilize closed-loop process obtains fuel oil after the organic solution is preferably fractionated into.
The specific steps and parameter of the fractionation are not particularly limited in the present invention, and those skilled in the art can be according to reality
Border production needs, processing requirement and quality requirement are selected and adjusted, and the fraction of fractionation of the present invention preferably includes 60
The heavy fuel oil ingredient of~180 DEG C of light Fuel oil ingredient and/or 180 DEG C or more, more preferably 60~180 DEG C of lightweight
The heavy fuel oil ingredient of fuel oil ingredient and 180 DEG C or more, i.e., the described organic solution preferably through two-part fractionating device, point
It She Ding not export, collect evaporating for 60 DEG C of following components, 60~180 DEG C of components and 180 DEG C or more component from upper, middle and lower end respectively
Point；Wherein described 60~180 DEG C of components may be used as light fuel oil, and 180 DEG C or more components act on heavy fuel oil.
The present invention is that complete and micronization processes process, above-mentioned steps are specifically as follows：
Organic solution is passed through into two-part fractionating device, set temperature collects 60 DEG C with the following group from upper, middle and lower end respectively
Point, the fraction of 60~180 DEG C of components and 180 DEG C or more component.Fractionating device is two sections of temperature, can be set according to experiment,
One entrance, three outlets, collects fraction.
The present invention is that further complete and micronization processes process, the processing step can be preferably integrally：
(1) decaying catalyst of recycling olefine aldehydr vapor phase method synthesis isoprene, autoclave is placed in by decaying catalyst
In, be added the catalyst such as solvent and Ru, Pd, Pt, Co, Ni or Ir, first check air-tightness whether gas leakage, then pass to nitrogen, set
It changes three times, then is passed through hydrogen, displacement three times, under certain reaction condition, carries out liquid phase method as reaction medium using organic solvent and adds hydrogen
Deoxygenation；
(2) after reaction, it is cooled to room temperature, opens kettle, reaction system, which is washed with water, removes acid, alcohol etc.；
(3) step 1~2 time of above-mentioned (1)~(2) are repeated；
(4) it after, is cooled to room temperature, separating catalyst and organic solution, catalyst are further dried in vacuo, after roasting
Cycle is for reacting；
(5) organic solution is passed through into two-part fractionating device, be set separately component 1 and 2 outlet temperature of component be 60 DEG C and
80 DEG C, the fraction of 60 DEG C of following components, 60~180 DEG C of components and 180 DEG C or more component is collected from upper, middle and lower end.
Referring to Fig. 1, Fig. 1 is the gas for the carbon deposition catalyst that olefine aldehydr vapor phase method provided by the invention synthesizes during isoprene
Phase chromatography-mass spectroscopy GC-MS analyzes collection of illustrative plates.
Above-mentioned steps of the present invention provide a kind of processing method of carbon deposition catalyst, are synthesized especially for olefine aldehydr vapor phase method
The carbon deposition catalyst of olefine aldehydr reaction is carried out hydrogenation deoxidation, then washes extraction by the processing method of the carbon deposition catalyst of isoprene
And separation finally carries out roasting activity recovery again to eliminate the organic principle of the overwhelming majority.The present invention is directed to olefine aldehydr gas phase
Carbon deposition catalyst is first placed in reaction under high pressure by the composition of method synthesis isoprene catalyst carbon deposition before catalyst roasting regeneration
It in kettle, is detached through the deoxidation of the catalyst to catalyzing hydrogenating such as Ru, Pd, Pt, Co, Ni or Ir, washing, fractionation, collection fraction obtains high attached
Value added fuel oil.The row of a large amount of hydrocarbons generated in carbon deposition catalyst roasting process can not only effectively be reduced
It puts, greatly reduces the pollution to environment, reduce cumbersome subsequent treatment process and processing cost, and that separates has
Machine liquid, additionally it is possible to handled by fractionation, obtain fuel oil, realize the closed loop process for comprehensive utilization of turning waste into wealth, not only environmental protection but also
Economy meets the sustainable development idea of environment-friendly and green.Meanwhile the processing method provided by the present invention, mild condition is quick, technique
Simply, at low cost, be conducive to industrialized production and popularization and application.
The experimental results showed that carbon deposition catalyst, in a solvent after hydrogenation reaction, carbon distribution content significantly reduces, after dry
Catalyst roasted, realize the regeneration of catalyst；And the organic solution obtained after hydrogenated reaction is alkanes.
In order to further illustrate the present invention, with reference to embodiments to a kind of processing of carbon deposition catalyst provided by the invention
Method is described in detail, but it is to be understood that and these embodiments are to be implemented down based on the technical solution of the present invention,
Detailed embodiment and specific operating process are given, are only the feature and advantage further illustrated the present invention, without
It is limiting to the claimed invention, protection scope of the present invention is also not necessarily limited to following embodiments.
Embodiment 1
Referring to Fig. 1, Fig. 1 is the gas for the carbon deposition catalyst that olefine aldehydr vapor phase method provided by the invention synthesizes during isoprene
Phase chromatography-mass spectroscopy GC-MS analyzes collection of illustrative plates.
As shown in Figure 1, the carbon deposition catalyst complicated component during olefine aldehydr vapor phase method synthesis isoprene, intractability
Greatly.
(1) take the carbon deposition catalyst generated during 110g olefine aldehydr vapor phase methods synthesis isoprene that 1.5L reaction kettles are added,
300ml dimethylbenzene and 20ml benzyl alcohols is added, adds 5g Ru/Al/SiO2(Ru load capacity 3wt%) closes reaction kettle, leads to
Enter high pure nitrogen and check whether gas leakage, entire reaction system is sealed, then three times with high pure nitrogen displacement, is passed through hydrogen, then set
It changes three times, adjusting pressure is 2.5MPa, is warming up to 150 DEG C and is stirred to react 2.5h, reaction terminates, and is cooled to room temperature；
(2) 500ml distilled water agitator treating organic solutions are added, water phase is detached after standing；
(3) it is primary that (1)~(2) are repeated；
(4) system obtained by (3), catalyst and organic solution separation, catalyst are placed in 65 DEG C of dry 4h in vacuum drying oven
Afterwards, then 500 DEG C roast 8h；
(5) organic solution of separation is passed through fractionating device, be set separately component 1 and 2 outlet temperature of component be 60 DEG C and
80 DEG C, 60 DEG C of following components of separation, 60~180 DEG C of components and 180 DEG C or more component are cooling respectively to collect each fraction.
Referring to Fig. 2, Fig. 2 is the fractionating device simplified schematic diagram of two-part provided by the invention fractionation.
Processing procedure in the embodiment of the present invention 1 is counted, separating obtained carbon deposition catalyst is 65 in step (4)
After DEG C drying, compared to the carbon distribution content of processing preceding 24%, carbon distribution content reduces 15%, reduces 62.5% on year-on-year basis, and 500 DEG C roast
Carbon distribution content is 0 after burning 8h；The separating obtained organic solution after adding hydrogen is alkanes in step (4).
Embodiment 2
(1) take the carbon deposition catalyst generated during 100g olefine aldehydr vapor phase methods synthesis isoprene that 1.5L reaction kettles are added,
300ml toluene and 30ml phenol is added, adds 5g Pt/SBA-15 (Pt load capacity 2wt%), closes reaction kettle, is passed through high-purity
Nitrogen checks whether gas leakage, and entire reaction system is sealed, then three times with high pure nitrogen displacement, is passed through hydrogen, then replace three times,
Adjusting pressure is 2.8MPa, is warming up to 160 DEG C and is stirred to react 3h, reaction terminates, and is cooled to room temperature；
(2) 500ml distilled water agitator treating organic solutions are added, water phase is detached after standing；
(3) it is primary that (1)~(2) are repeated；
(4) system obtained by (3), catalyst and organic solution separation, catalyst are placed in 70 DEG C of dry 4h in vacuum drying oven
Afterwards, then 550 DEG C roast 5h；
(5) organic solution of separation is passed through fractionating device, 60 DEG C of following components of separation, 60~180 DEG C of components and 180 DEG C
The above component, it is cooling respectively to collect each fraction.
Processing procedure in the embodiment of the present invention 2 is counted, separating obtained carbon deposition catalyst is 70 in step (4)
After DEG C drying, compared to the carbon distribution content of processing preceding 24%, carbon distribution content reduces 19%, reduces 79.2% on year-on-year basis, and 550 DEG C roast
Carbon distribution content is 0 after burning 5h；The separating obtained organic solution after adding hydrogen is alkanes in step (4).
Embodiment 3
(1) take the carbon deposition catalyst generated during 110g olefine aldehydr vapor phase methods synthesis isoprene that 1.5L reaction kettles are added,
300ml toluene and 10ml benzyl alcohols is added, adds 5g Pd/ZSM-5 (Pd load capacity 1.5wt%), closes reaction kettle, is passed through
High pure nitrogen checks whether gas leakage, and entire reaction system is sealed, then three times with high pure nitrogen displacement, is passed through hydrogen, then replace
Three times, it is 3.0MPa to adjust pressure, is warming up to 170 DEG C and is stirred to react 3.5h, reaction terminates, and is cooled to room temperature；
(2) 500ml distilled water agitator treating organic solutions are added, water phase is detached after standing；
(3) (1)~(2) are repeated twice；
(4) system obtained by (3), catalyst and organic solution separation, catalyst are placed in 75 DEG C of dry 5h in vacuum drying oven
Afterwards, then 520 DEG C roast 6h；
(5) organic solution of separation is passed through fractionating device, 60 DEG C of following components of separation, 60~180 DEG C of components and 180 DEG C
The above component, it is cooling respectively to collect each fraction.
Processing procedure in the embodiment of the present invention 3 is counted, 75 DEG C separating obtained of carbon deposition catalyst in step (4)
After drying, compared to the carbon distribution content of processing preceding 24%, carbon distribution content reduces 14%, reduces 58.3% on year-on-year basis, 520 DEG C of roastings
Carbon distribution content is 0 after 6h；(4) the separating obtained organic solution after adding hydrogen is alkanes in.
Embodiment 4
(1) take the carbon deposition catalyst generated during 120g olefine aldehydr vapor phase methods synthesis isoprene that 1.5L reaction kettles are added,
300ml dimethylbenzene and 30ml benzyl alcohols is added, adds 5g Ni/SAPO (Ni load capacity 2.5wt%), closes reaction kettle, is passed through
High pure nitrogen checks whether gas leakage, and entire reaction system is sealed, then three times with high pure nitrogen displacement, is passed through hydrogen, then replace
Three times, it is 2.5MPa to adjust pressure, is warming up to 145 DEG C and is stirred to react 4h, reaction terminates, and is cooled to room temperature；
(2) 500ml distilled water agitator treating organic solutions are added, water phase is detached after standing；
(3) it is primary that (1)~(2) are repeated；
(4) system obtained by (3), catalyst and organic solution separation, catalyst are placed in 65 DEG C of dry 5h in vacuum drying oven
Afterwards, then 530 DEG C roast 8h；
(5) organic solution of separation is passed through fractionating device, 60 DEG C of following components of separation, 60~180 DEG C of components and 180 DEG C
The above component, it is cooling respectively to collect each fraction.
Processing procedure in the embodiment of the present invention 4 is counted, 65 DEG C separating obtained of carbon deposition catalyst in step (4)
After drying, compared to the carbon distribution content of processing preceding 24%, carbon distribution content reduces 17%, reduces 70.8% on year-on-year basis, 530 DEG C of roastings
Carbon distribution content is 0 after 8h；(4) the separating obtained organic solution after adding hydrogen is alkanes in.
Embodiment 5
(1) it takes the carbon deposition catalyst generated during 90g olefine aldehydr vapor phase methods synthesis isoprene that 1.5L reaction kettles are added, adds
Enter 300ml dimethylbenzene and 10ml benzyl alcohols, adds 5g Co/Zr/SiO2(Co load capacity 1.0wt%) closes reaction kettle, leads to
Enter high pure nitrogen and check whether gas leakage, entire reaction system is sealed, then three times with high pure nitrogen displacement, is passed through hydrogen, then set
It changes three times, adjusting pressure is 2.5MPa, is warming up to 155 DEG C and is stirred to react 4h, reaction terminates, and is cooled to room temperature；
(2) 500ml distilled water agitator treating organic solutions are added, water phase is detached after standing；
(3) (1)~(2) are repeated twice；
(4) system obtained by (3), catalyst and organic solution separation, catalyst are placed in 75 DEG C of dry 6h in vacuum drying oven
Afterwards, then 550 DEG C roast 8h；
(5) organic solution of separation is passed through fractionating device, 60 DEG C of following components of separation, 60~180 DEG C of components and 180 DEG C
The above component, it is cooling respectively to collect each fraction.
Processing procedure in the embodiment of the present invention 5 is counted, 75 DEG C separating obtained of carbon deposition catalyst in step (4)
After drying, compared to the carbon distribution content of processing preceding 24%, carbon distribution content reduces 10%, reduces 41.7% on year-on-year basis, 550 DEG C of roastings
Carbon distribution content is 0 after 8h；(4) the separating obtained organic solution after adding hydrogen is alkanes in.
Embodiment 6
(1) it takes the carbon deposition catalyst generated during 80g olefine aldehydr vapor phase methods synthesis isoprene that 1.5L reaction kettles are added, adds
Enter 300ml dimethylbenzene and 10ml benzyl alcohols, adds 5g Ir/Al/SiO2(Ir load capacity 2.5wt%) closes reaction kettle, leads to
Enter high pure nitrogen and check whether gas leakage, entire reaction system is sealed, then three times with high pure nitrogen displacement, is passed through hydrogen, then set
It changes three times, adjusting pressure is 3.0MPa, is warming up to 165 DEG C and is stirred to react 3.5h, reaction terminates, and is cooled to room temperature；
(2) 500ml distilled water agitator treating organic solutions are added, water phase is detached after standing；
(3) (1)~(2) are repeated twice；
(4) system obtained by (3), catalyst and organic solution separation, catalyst are placed in 75 DEG C of dry 6h in vacuum drying oven
Afterwards, then 550 DEG C roast 8h；
(5) organic solution of separation is passed through fractionating device, 60 DEG C of following components of separation, 60~180 DEG C of components and 180 DEG C
The above component, it is cooling respectively to collect each fraction.
Processing procedure in the embodiment of the present invention 6 is counted, 75 DEG C separating obtained of carbon deposition catalyst in step (4)
After drying, compared to the carbon distribution content of processing preceding 24%, carbon distribution content reduces 16%, reduces 66.7% on year-on-year basis, 550 DEG C of roastings
Carbon distribution content is 0 after 8h；(4) the separating obtained organic solution after adding hydrogen is alkanes in.
Above to olefine aldehydr vapor phase method provided by the invention synthesis isoprene generate carbon deposition catalyst processing method into
Detailed introduction is gone, principle and implementation of the present invention are described for specific case used herein, the above reality
The explanation for applying example is merely used to help understand the method and its core concept of the present invention, including best mode, and but also originally
Any technical staff in field can put into practice the present invention, including manufacture and use any device or system, and implement any knot
The method of conjunction.It should be pointed out that for those skilled in the art, in the premise for not departing from the principle of the invention
Under, it can be with several improvements and modifications are made to the present invention, these improvement and modification also fall into the protection of the claims in the present invention
In range.The range of patent protection of the present invention is defined by the claims, and may include those skilled in the art it is conceivable that
Other embodiment.If these other embodiments have the structural element for being not different from claim character express, or
If they include and equivalent structural elements of the character express of claim without essence difference, these other embodiments
Should include within the scope of the claims.
Claims (10)
1. a kind of processing method of carbon deposition catalyst, which is characterized in that include the following steps：
1) under conditions of hydrogen, after carbon deposition catalyst, catalyst and organic solvent are reacted, reaction system is obtained, then
After being washed to reaction system, solidliquid mixture is obtained；
2) after being detached the solidliquid mixture that above-mentioned steps obtain, solid and organic solution are obtained；
3) after the solid that above-mentioned steps obtain being roasted, the regenerated catalyst that obtains that treated.
2. processing method according to claim 1, which is characterized in that the catalyst is metallic catalyst；
The metal includes one or more in Ru, Pd, Pt, Co, Ni and Ir；
The carbon deposition catalyst is the carbon deposition catalyst that olefine aldehydr vapor phase method synthesizes that isoprene generates.
3. processing method according to claim 1, which is characterized in that the catalyst is loaded catalyst；
The load capacity is 0.1%~5%；
The carrier is acid carrier.
4. processing method according to claim 3, which is characterized in that the organic solvent includes toluene, paraxylene, neighbour
It is one or more in dimethylbenzene, phenol, hydroquinone, benzyl alcohol and hexamethylene；
The acid carrier includes SBA-15, ZSM-5, X-type molecular sieve, Y type molecular sieve, beta-molecular sieve, SAPO molecular sieve, Al/
SiO2、Al2O3、Zr/SiO2And ZrO2In it is one or more.
5. processing method according to claim 1, which is characterized in that the mass ratio of the catalyst and carbon deposition catalyst is
1：(10~30)；
The pressure of the hydrogen is 2.0~4.0MPa；
The volume ratio of the carbon deposition catalyst and organic solvent is 1：(1.8~2.5).
6. processing method according to claim 1, which is characterized in that the step 1) can carry out 1 time, or repeat
1~3 time；
The temperature of the reaction is 130~200 DEG C；
The time of the reaction is 1.5~5h.
7. processing method according to claim 1, which is characterized in that the temperature of the roasting is 450~600 DEG C；
The time of the roasting is 3~10h.
8. processing method according to claim 1, which is characterized in that further include drying steps before the roasting；
The temperature of the drying is 60~80 DEG C；
The time of the drying is 3~10h.
9. according to the processing method described in claim 1~8 any one, which is characterized in that after the organic solution is fractionated into,
Obtain fuel oil.
10. processing method according to claim 1, which is characterized in that the fraction of the fractionation includes 60~180 DEG C light
The heavy fuel oil ingredient of matter fuel oil ingredient and/or 180 DEG C or more.
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