CN108636348A - The method for loading adsorbent of basic active component and preparation method thereof and depth dechlorination - Google Patents

The method for loading adsorbent of basic active component and preparation method thereof and depth dechlorination Download PDF

Info

Publication number
CN108636348A
CN108636348A CN201810379910.3A CN201810379910A CN108636348A CN 108636348 A CN108636348 A CN 108636348A CN 201810379910 A CN201810379910 A CN 201810379910A CN 108636348 A CN108636348 A CN 108636348A
Authority
CN
China
Prior art keywords
adsorbent
basic active
dechlorination
molecular sieve
active component
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.)
Granted
Application number
CN201810379910.3A
Other languages
Chinese (zh)
Other versions
CN108636348B (en
Inventor
周广林
李芹
吴全贵
王晓胜
周红军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing Zhong Shi Great New Forms Of Energy Research Institute Co Ltd
China University of Petroleum Beijing
Original Assignee
Beijing Zhong Shi Great New Forms Of Energy Research Institute Co Ltd
China University of Petroleum Beijing
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Beijing Zhong Shi Great New Forms Of Energy Research Institute Co Ltd, China University of Petroleum Beijing filed Critical Beijing Zhong Shi Great New Forms Of Energy Research Institute Co Ltd
Priority to CN201810379910.3A priority Critical patent/CN108636348B/en
Publication of CN108636348A publication Critical patent/CN108636348A/en
Application granted granted Critical
Publication of CN108636348B publication Critical patent/CN108636348B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
    • 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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
    • 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
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The present invention provides a kind of method of the adsorbent and preparation method thereof and depth dechlorination of load basic active component.It is 100% meter according to weight, the adsorbent of the load basic active component includes the basic active metal component of 30% 70% molecular sieve, 10% 50% activated alumina and surplus.The sorbent preparation method is：By molecular sieve, binder and pore creating material kneading and compacting, adsorbing agent carrier is prepared after drying and roasting；Adsorbing agent carrier is impregnated in the aqueous solution dipping of basic active metal component, the adsorbent of the load basic active component is obtained after filtration drying roasting.The adsorbent of load basic active component provided by the invention is applied in the ionic liquid allcylation oil dechlorination process of fixed-bed process, dechlorination effect is excellent, adsorbent reactivation process is simple and effective, low energy consumption, hydrogen is not needed, the ionic liquid allcylation oil after the technique dechlorination can be directly as gasoline ready-mixed oil.

Description

The method for loading adsorbent of basic active component and preparation method thereof and depth dechlorination
Technical field
The invention belongs to alkylate oil dechlorination technology fields, and in particular to it is a kind of load basic active component adsorbent and its Preparation method and using the adsorbent carry out ionic liquid allcylation oil depth dechlorination method.
Background technology
Alkylate oil is a kind of common high-knock rating gasoline blend component, has octane number high, susceptibility is good, vapour pressure Low, boiling spread is wide, not olefin-containing and the advantages that aromatic hydrocarbons and combustion cleaning, and generally the chain type by isoparaffin and alkene is anti- It should generate.Current gasoline standard is continuously improved, Aromatic Hydrocarbon in Gasoline and gradual stringent, the importance of alkylate oil of olefin(e) centent limitation It is increasingly prominent.Conventional alkylation reaction is broadly divided into sulfuric acid process alkylation techniques and hydrogen fluoride alkylation techniques, but the two is all The problems such as there is insoluble serious equipment corrosion and environmental pollutions, significantly limits its wide popularization and application.From Sub- liquid is a kind of emerging environmental-friendly fluent material being made of completely zwitterion.Due to its unique physical chemistry Matter, such as extremely low vapour pressure, wide in range liquid temperature range, good solvability, the designability of specific function, in alkane The extensive concern of domestic and international many scholars is caused in terms of glycosylation reaction catalysis.But ionic liquid allcylation is in some cases Chloro the hydrocarbon component can be introduced in alkylate oil.If this kind of alkylate oil can generate unfavorable by-product directly as fuel combustion Object such as HCl, so as to cause corrosion.Therefore, it is necessary organochlorine to be removed from this kind of alkylate oil.
However, including in the prior art mainly hydrogenation and removing method, phase transfer catalyst to ionic liquid allcylation oil dechlorination Removal method, adsorbing and removing method etc..But the reaction condition of the high temperature and pressure of hydrogenation-dechlorination increase whole operation danger and Complexity limits its development；In addition, needing to consume a large amount of hydrogen during hydrogenation-dechlorination.Phase transfer catalyst removes Method used catalyst price is relatively high；There are process route length, high energy consumption, investments for common absorption dechlorination method greatly, and The defects of commercial introduction is difficult.
Invention content
Based on the defect of ionic liquid allcylation oil dechlorination in the prior art, the purpose of the present invention is to provide a kind of loads The adsorbent and preparation method thereof of basic active component；The sorbent preparation method is simple, and dechlorination effect is good.The purpose of the present invention is also It is to provide the method for carrying out depth dechlorination to ionic liquid allcylation oil using the adsorbent, utilizes the adsorbent and dechlorination work Ionic liquid allcylation oil after skill can be directly as gasoline blend component.
The purpose of the present invention is achieved by the following technical programs：
On the one hand, the present invention provides a kind of adsorbent of load basic active component, is 100% meter, the load according to weight The adsorbent of basic active component includes the basic active of the molecular sieve of 30%-70%, the activated alumina of 10%-50% and surplus Metal component.
In above-mentioned adsorbent, it is preferable that the specific surface area of the adsorbent of the load basic active component is 200-550m2/ G, Kong Rongwei 0.20-0.40cm3/ g, bulk density 0.50-0.70g/cm3。
In above-mentioned adsorbent, it is preferable that the molecular sieve may include A type molecular sieve, X-type molecular sieve, Y type molecules One or more combinations in sieve, ZSM Series Molecules sieve and MCM Series Molecules sieve etc.；
The A type molecular sieve may include one or more groups in 3A molecular sieves, 4A molecular sieves and 5A molecular sieves etc. It closes；The X-type molecular sieve may include 13X molecular sieves and/or 10X molecular sieves etc.；The Y type molecular sieve may include NaY points Son sieve and/or HY molecular sieves etc.；ZSM Series Molecules sieve may include ZSM-5 molecular sieve, ZSM-8 molecular sieves, ZSM-11 points One or more combinations in son sieve and ZSM-35 molecular sieve etc.；The MCM Series Molecules sieve may include MCM-22 molecules Sieve and/or MCM-41 molecular sieves etc..
In above-mentioned adsorbent, it is preferable that the molecular sieve may include NaY molecular sieve, 13X molecular sieves, HX molecular sieves With one or more combinations in ZSM-5 molecular sieve etc.；Preferably, the molecular sieve includes 13X molecular sieves.
In above-mentioned adsorbent, it is preferable that the basic active metal component can be IA races metal or Group IIA metal；It is excellent Selection of land, the basic active metal component may include one or more combinations in potassium, sodium, magnesium and calcium etc.；Preferably, described Basic active metal component includes one or more combinations in potassium, sodium and magnesium.
On the other hand, the present invention also provides the preparation methods of the adsorbent of above-mentioned load basic active component comprising following Step：
Molecular sieve, binder and pore creating material kneading and compacting are prepared adsorbing agent carrier by step 1 after drying and roasting；
Step 2, the aqueous solution that adsorbing agent carrier is impregnated in basic active metal component impregnate, and are obtained after filtration drying roasting Obtain the adsorbent of the load basic active component.In above-mentioned preparation method, it is preferable that the binder preparation method is：By hydrogen Aluminium oxide is uniformly mixed with peptizing agent is prepared the binder.
In above-mentioned preparation method, it is preferable that the peptizing agent may include inorganic acid, organic acid and strong acid cation ion One or more combinations in salt etc..
In above-mentioned preparation method, it is preferable that the inorganic acid may include one kind in nitric acid, hydrochloric acid and sulfuric acid etc. or A variety of combinations.
In above-mentioned preparation method, it is preferable that the organic acid may include in formic acid, acetic acid, oxalic acid and citric acid etc. One or more combinations.
In above-mentioned preparation method, it is preferable that the strong acid cation ion salt may include aluminum nitrate etc..
In above-mentioned preparation method, it is preferable that the pore creating material may include carbon black, sesbania powder, carboxymethyl cellulose and One or more combinations in higher alcohols etc..Pore creating material can be used for assisting aluminium hydroxide extrusion forming.
In above-mentioned preparation method, it is preferable that the aqueous solution of the basic active metal component may include that potassium carbonate is water-soluble Liquid etc..
In above-mentioned preparation method, it is preferable that in step 1, dry temperature is 100-120 DEG C, and the dry time is 8-15h；The temperature of roasting is 490-630 DEG C, and the time of roasting is 4-8h.
In above-mentioned preparation method, it is preferable that in step 2, the time of dipping is 5-10h；Dry temperature is 90- 120 DEG C, the dry time is 8-13h；The temperature of roasting is 490-630 DEG C, and the time of roasting is 4-8h.
In the adsorbent of the load basic active component of the present invention, the micropore of the molecular sieve of use is to the chlorination in alkylate oil Object has stronger adsorption selectivity.After alkali modification, adsorbent forms secondary mesopore structure, and it is logical to be more advantageous to chloride It crosses diffusion to contact with the activated centre in adsorbent duct, improves the adsorption capacity of adsorbent.
In another aspect, the present invention also provides a kind of methods of the depth dechlorination of ionic liquid allcylation oil comprising following Step：
Using fixed bed reactors, the fixed bed reactors include at least two and are connected；The fixed bed is anti- Answer the adsorbent for loading above-mentioned load basic active component in device on bed；
Ionic liquid allcylation oil is passed through in first fixed bed reactors progress dechlorination processing, after adsorption penetration from Sub- liquid alkyl carburetion is passed through again into another fixed bed reactors being connected with first fixed bed reactors and carries out Further dechlorination processing.
In the method for above-mentioned depth dechlorination, it is preferable that this method further includes the steps that carrying out following regeneration to adsorbent：
Adsorbent reactivation of the vapor to load basic active component, regeneration are passed through into the fixed bed reactors of adsorption saturation Stop being passed through vapor after the completion, and processing is dried to the adsorbent for loading basic active component using nitrogen, to obtain The adsorbent of load basic active component after regeneration.
In the method for above-mentioned depth dechlorination, it is preferable that carry out absorption dechlorination condition be：Temperature in fixed bed reactors Degree is 0-50 DEG C, pressure 0.5-2.0MPa；The air speed of ionic liquid allcylation oil is 0.25-4h-1。
In the method for above-mentioned depth dechlorination, it is preferable that the condition for carrying out adsorbent reactivation is：In fixed bed reactors Temperature is 100-180 DEG C, pressure 0.1-0.5MPa；The air speed of vapor is 30-1000h-1。
The adsorbent of load basic active component using the present invention carries out depth dechlorination to ionic liquid allcylation oil, passes through The microporous molecular sieve of adsorbent has stronger adsorption selectivity to the chloride in alkylate oil；Dosage form is adsorbed after alkali modification At secondary mesopore structure, it is more advantageous to chloride and is contacted with the activated centre in adsorbent duct by spreading, improve adsorbent Adsorption capacity.
The adsorbent of load basic active component provided by the invention is applied to the ionic liquid allcylation oil of fixed-bed process In dechlorination process, dechlorination effect is excellent, and adsorbent reactivation process is simple and effective, and low energy consumption, does not need hydrogen；It is de- by the technique Ionic liquid allcylation oil after chlorine can be directly as gasoline ready-mixed oil.
Specific implementation mode
In order to which technical characteristic, purpose and the advantageous effect to the present invention are more clearly understood, now to the skill of the present invention Art scheme carry out it is described further below, but should not be understood as to the present invention can practical range restriction.
Specific surface area and Kong Rong are using low temperature liquid nitrogen determination of adsorption method in the method for the present invention.Ionic liquid allcylation oil Middle chlorinity analysis uses coulomb chlorine analysis method.
Embodiment 1
The present embodiment provides a kind of preparation methods of the adsorbent of load basic active component comprising following steps：
Take aluminium hydroxide (specific surface area 230m2/ g, hole hold 0.65cm3/ g) 55.0g, 45.0g distilled water and 6.5mL is added Concentrated nitric acid is uniformly mixed, makes binder.Take 13X molecular screen primary powders (silica alumina ratio 2.1) 94.5g, sesbania powder 3.0g and above-mentioned Binder kneading, extruded moulding, wet bar is 12 hours dry at 110 DEG C, is roasted 4 hours at 550 DEG C, and adsorbent load is made Body.
It takes 29.5g potassium carbonate to distill water dissolution, is made into 110mL solution, above-mentioned adsorbing agent carrier is added in maceration extract, Dipping 6 hours, is then filtered, 10 hours dry at 110 DEG C, is roasted 4 hours at 550 DEG C, and load basic active metal is made The adsorbent A of component.
The embodiment prepare load basic active metal component adsorbent A include 61.6% 13X molecular sieves, 25.3% aluminium oxide and 13.1% basic active metal component potassium；The specific surface area of the adsorbent A is 360m2/ g, Kong Rongwei 0.35cm3/ g, bulk density 0.52g/cm3。
The present embodiment also provides the technique for carrying out depth dechlorination to ionic liquid allcylation oil using above-mentioned adsorbent A, packet Include following steps：
The solid-state amount of the adsorbent A 30mL of the above-mentioned load basic active component prepared is fitted into fixed bed reactors, In 25 DEG C, reaction pressure 0.5MPa of reaction temperature, feed volume air speed 1.0h-1Under conditions of, use chlorinity for 350ppm's Ionic liquid allcylation oil is that raw material carries out absorption dechlorination, and raw material, which mainly forms, to be shown in Table 1 (following embodiment is all made of identical original Material), the chlorine in the oil of ionic liquid allcylation is adsorbed on bed by organic chloride form and such as table 2.When load basic active group After the adsorbent adsorption penetration divided；It switches to another reactor and carries out absorption dechlorination, while drawing into the reactor after penetrating Enter vapor, 150 DEG C, pressure 0.2MPa in regeneration temperature, air speed (vapor) 50h-1Under conditions of, to loading basic active group The adsorbent divided carries out gas phase regeneration in 10 hours, then with 200h at 400 DEG C-1Air speed be passed through nitrogen 40 hours to bed. Dechlorination result such as table 3, table 4 after the adsorbent reactivation of dechlorination result and load basic active component.
Table 1：
Composition Ionic liquid allcylation oil (volume content)
Isooctane 97.0
Normal butane 3.0
Table 2：
Chlorine form Content/ppmw
Sec-Butyl Chloride 280
2- chloroethene -2- methyl-propans 43.7
Chloroform 20.6
It is other 5.7
Embodiment 2
The present embodiment provides a kind of preparation methods of the adsorbent of load basic active component comprising following steps：
Take aluminium hydroxide (specific surface area 210m2/ g, hole hold 0.75cm3/ g) 55.0g, 45.0g distilled water and 6.5mL is added Concentrated nitric acid is uniformly mixed, makes binder.Take 13X molecular screen primary powders (silica alumina ratio 1.0) 94.5g, sesbania powder 2.0g and above-mentioned Binder kneading, extruded moulding, wet bar is 12 hours dry at 110 DEG C, is roasted 4 hours at 550 DEG C, and adsorbent load is made Body.
It takes 29.5g potassium carbonate to distill water dissolution, is made into 110mL solution, above-mentioned adsorbing agent carrier is added in maceration extract, Dipping 6 hours, is then filtered, 10 hours dry at 110 DEG C, is roasted 4 hours at 550 DEG C, and load basic active component is made Adsorbent B.
The embodiment prepare load basic active metal component adsorbent B include 61.9% 13X molecular sieves, 24.9% aluminium oxide and 13.2% basic active metal component potassium；The specific surface area of the adsorbent B is 353m2/ g, Kong Rongwei 0.34cm3/ g, bulk density 0.53g/cm3。
The present embodiment also provides the technique for carrying out depth dechlorination to ionic liquid allcylation oil using above-mentioned adsorbent B, packet Include following steps：
The solid-state amount of the adsorbent B 30mL of the above-mentioned load basic active component prepared is fitted into fixed bed reactors, In 25 DEG C, reaction pressure 0.5MPa of reaction temperature, feed volume air speed 2.0h-1Under conditions of, use chlorinity for 350ppm's Ionic liquid allcylation oil is that raw material carries out absorption dechlorination, and the chlorine in the oil of ionic liquid allcylation is adsorbed on bed.When negative After the adsorbent adsorption penetration for carrying basic active component, switches to another reactor and carry out absorption dechlorination, while to after penetrating Vapor is introduced in reactor, in 130 DEG C, pressure 0.2MPa of regeneration temperature, air speed (vapor) 100h-1Under conditions of, to negative The adsorbent for carrying basic active component carries out gas phase regeneration in 9 hours, then with 200h at 400 DEG C-1Air speed be passed through nitrogen to bed Gas 40 hours.Dechlorination result such as table 3, table 4 after the adsorbent reactivation of dechlorination result and load basic active component.
Embodiment 3
The present embodiment provides a kind of preparation methods of the adsorbent of load basic active component comprising following steps：
Take aluminium hydroxide (specific surface area 230m2/ g, hole hold 0.65cm3/ g) 55.0g, 45.0g distilled water and 6.5mL is added Concentrated nitric acid is uniformly mixed, makes binder.Take 13X molecular screen primary powders (silica alumina ratio 5) 94.5g, sesbania powder 3.0g and above-mentioned viscous Agent kneading is tied, extruded moulding, wet bar is 12 hours dry at 110 DEG C, is roasted 4 hours at 550 DEG C, adsorbing agent carrier is made.
It takes 29.5g potassium carbonate to distill water dissolution, is made into 110mL solution, above-mentioned adsorbing agent carrier is added in maceration extract, Dipping 6 hours, is then filtered, 10 hours dry at 110 DEG C, is roasted 4 hours at 550 DEG C, and load basic active component is made Adsorbent C.
The embodiment prepare load basic active metal component adsorbent C include 61.5% 13X molecular sieves, 25.3% aluminium oxide and 13.2% basic active metal component potassium；The specific surface area of adsorbent C is 349m2/ g, Kong Rongwei 0.32cm3/ g, bulk density 0.55g/cm3。
The present embodiment also provides the technique for carrying out depth dechlorination to ionic liquid allcylation oil using above-mentioned adsorbent C, packet Include following steps：
The solid-state amount of the adsorbent C 30mL of the above-mentioned load basic active component prepared is fitted into fixed bed reactors, In 25 DEG C, reaction pressure 0.5MPa of reaction temperature, feed volume air speed 1.0h-1Under conditions of, use chlorinity for 350ppm's Ionic liquid allcylation oil is that raw material carries out absorption dechlorination, and the chlorine in the oil of ionic liquid allcylation is adsorbed on bed.When negative After the adsorbent adsorption penetration for carrying basic active component, switches to another reactor and carry out absorption dechlorination, while to after penetrating Vapor is introduced in reactor, in 110 DEG C, pressure 0.2MPa of regeneration temperature, air speed (vapor) 30h-1Under conditions of, to load The adsorbent of basic active component carries out gas phase regeneration in 12 hours, then with 200h at 400 DEG C-1Air speed be passed through nitrogen to bed 40 hours.Dechlorination result such as table 3, table 4 after the adsorbent reactivation of dechlorination result and load basic active component.
Embodiment 4
The present embodiment provides a kind of preparation methods of the adsorbent of load basic active component comprising following steps：
Take aluminium hydroxide (specific surface area 230m2/ g, hole hold 0.65cm3/ g) 55.0g, 45.0g distilled water and 6.5mL is added Concentrated nitric acid is uniformly mixed, makes binder.Take ZSM-5 molecular sieve (silica alumina ratio 30) 94.5g, sesbania powder 3.0g and above-mentioned viscous Agent kneading is tied, extruded moulding, wet bar is 12 hours dry at 110 DEG C, is roasted 4 hours at 550 DEG C, adsorbing agent carrier is made.
It takes 29.5g potassium carbonate to distill water dissolution, is made into 110mL solution, above-mentioned adsorbing agent carrier is added in maceration extract, Dipping 6 hours, is then filtered, 10 hours dry at 110 DEG C, is roasted 4 hours at 550 DEG C, and load basic active component is made Adsorbent D.
The embodiment prepare load basic active metal component adsorbent D include 61.5% ZSM-5 molecular sieve, 25.5% aluminium oxide and 13% basic active metal component potassium；The specific surface area of adsorbent D is 330m2/ g, Kong Rongwei 0.29cm3/ g, bulk density 0.59g/cm3。
The present embodiment also provides the technique for carrying out depth dechlorination to ionic liquid allcylation oil using above-mentioned adsorbent D, packet Include following steps：
The solid-state amount of the adsorbent D 30mL of the above-mentioned load basic active component prepared is fitted into fixed bed reactors, In 25 DEG C, reaction pressure 0.5MPa of reaction temperature, feed volume air speed 1.0h-1Under conditions of, use chlorinity for 350ppm's Ionic liquid allcylation oil is that raw material carries out absorption dechlorination, and the chlorine in the oil of ionic liquid allcylation is adsorbed on bed.When negative After the adsorbent adsorption penetration for carrying basic active component, switches to another reactor and carry out absorption dechlorination, while to after penetrating Vapor is introduced in reactor, in 110 DEG C, pressure 0.2MPa of regeneration temperature, air speed (vapor) 80h-1Under conditions of, to load The adsorbent of basic active component carries out gas phase regeneration in 8 hours, then with 200h at 400 DEG C-1Air speed be passed through nitrogen to bed 40 hours.Dechlorination result such as table 3, table 4 after the adsorbent reactivation of dechlorination result and load basic active component.
Embodiment 5
The present embodiment provides a kind of preparation methods of the adsorbent of load basic active component comprising following steps：
Take aluminium hydroxide (specific surface area 230m2/ g, hole hold 0.65cm3/ g) 55.0g, 45.0g distilled water and 6.5mL is added Concentrated nitric acid is uniformly mixed, makes binder.Take NaY molecular sieve (silica alumina ratio 5) 94.5g, sesbania powder 3.0g and above-mentioned binder Kneading, extruded moulding, wet bar is 12 hours dry at 110 DEG C, is roasted 4 hours at 550 DEG C, adsorbing agent carrier is made.
It takes 29.5g potassium carbonate to distill water dissolution, is made into 110mL solution, above-mentioned adsorbing agent carrier is added in maceration extract, Dipping 6 hours, is then filtered, 10 hours dry at 110 DEG C, is roasted 4 hours at 550 DEG C, and load basic active component is made Adsorbent E.
The embodiment prepare load basic active metal component adsorbent E include 60.9% NaY molecular sieve, 25.9% aluminium oxide and 13.2% basic active metal component potassium；The specific surface area of adsorbent E is 341m2/ g, Kong Rongwei 0.29cm3/ g, bulk density 0.59g/cm3。
The present embodiment also provides the technique for carrying out depth dechlorination to ionic liquid allcylation oil using above-mentioned adsorbent E, packet Include following steps：
The solid-state amount of the adsorbent E 30mL of the above-mentioned load basic active component prepared is fitted into fixed bed reactors, In 25 DEG C, reaction pressure 0.5Mpa of reaction temperature, feed volume air speed 1.0h-1Under conditions of, use chlorinity for 350ppm's Ionic liquid allcylation oil is that raw material carries out absorption dechlorination, and the chlorine in the oil of ionic liquid allcylation is adsorbed on bed.When negative After the adsorbent adsorption penetration for carrying basic active component, switches to another reactor and carry out absorption dechlorination, while to after penetrating Vapor is introduced in reactor, in 110 DEG C, pressure 0.2Mpa of regeneration temperature, air speed (vapor) 30h-1Under conditions of, to load The adsorbent of basic active component carries out gas phase regeneration in 15 hours, then with 200h at 400 DEG C-1Air speed be passed through nitrogen to bed 40 hours.Dechlorination result such as table 3, table 4 after the adsorbent reactivation of dechlorination result and load basic active component.
Table 3：
Table 4：
From 4 experimental data of table 3 and table：Under the same operating conditions, the adsorbent of alkali metals modified can incite somebody to action Near 2ppm of chlorine of 350ppm or so, dechlorination it is good, while it can be seen from Table 4 that adsorbent have good regeneration Performance, the active group instinct of adsorbent is restored to the level of fresh adsorbent after regeneration, so the production after adsorbent dechlorination Product can be used directly to as gasoline ready-mixed oil.
In conclusion the adsorbent of load basic active component provided by the invention is applied to the ionic liquid of fixed-bed process In alkylate oil dechlorination process, dechlorination effect is excellent, and adsorbent reactivation process is simple and effective, and low energy consumption, does not need hydrogen；By Ionic liquid allcylation oil after the technique dechlorination can be directly as gasoline ready-mixed oil.

Claims (10)

1. a kind of adsorbent of load basic active component, it is characterised in that：It is 100% meter, the load basic active group according to weight The adsorbent divided includes the basic active metal group of the molecular sieve of 30%-70%, the activated alumina of 10%-50% and surplus Point.
2. adsorbent according to claim 1, it is characterised in that：The specific surface area of the adsorbent of the load basic active component For 200-550m2/ g, Kong Rongwei 0.20-0.40cm3/ g, bulk density 0.50-0.70g/cm3。
3. adsorbent according to claim 1 or 2, it is characterised in that：The molecular sieve includes A type molecular sieve, X-type molecule One or more combinations in sieve, Y type molecular sieve, ZSM Series Molecules sieve and MCM Series Molecules sieve；
The A type molecular sieve includes one or more combinations in 3A molecular sieves, 4A molecular sieves and 5A molecular sieves；The X-type Molecular sieve includes 13X molecular sieves and/or 10X molecular sieves；The Y type molecular sieve includes NaY molecular sieve and/or HY molecular sieves；Institute It includes one kind in ZSM-5 molecular sieve, ZSM-8 molecular sieves, ZSM-11 molecular sieves and ZSM-35 molecular sieve to state ZSM Series Molecules sieve Or a variety of combination；The MCM Series Molecules sieve includes MCM-22 molecular sieves and/or MCM-41 molecular sieves；
Preferably, the molecular sieve include NaY molecular sieve, 13X molecular sieves, HX molecular sieves and one kind in ZSM-5 molecular sieve or A variety of combinations；Preferably, the molecular sieve includes 13X molecular sieves.
4. adsorbent according to claim 1 or 2, it is characterised in that：The basic active metal component be IA races metal or Group IIA metal；Preferably, the basic active metal component includes one or more combinations in potassium, sodium, magnesium and calcium；It is preferred that Ground, the basic active metal component include one or more combinations in potassium, sodium and magnesium.
5. the preparation method of the adsorbent of any one of the claim 1-4 load basic active components comprising following steps：
Molecular sieve, binder and pore creating material kneading and compacting are prepared adsorbing agent carrier by step 1 after drying and roasting；
Step 2, the aqueous solution that adsorbing agent carrier is impregnated in basic active metal component impregnate, and are somebody's turn to do after filtration drying roasting Load the adsorbent of basic active component.
6. preparation method according to claim 5, it is characterised in that：The binder preparation method is：By aluminium hydroxide It is uniformly mixed with peptizing agent and the binder is prepared；
Preferably, the peptizing agent includes one or more combinations in inorganic acid, organic acid and strong acid cation ion salt；
Preferably, the inorganic acid includes one or more combinations in nitric acid, hydrochloric acid and sulfuric acid；
Preferably, the organic acid includes one or more combinations in formic acid, acetic acid, oxalic acid and citric acid；
Preferably, the strong acid cation ion salt includes aluminum nitrate；
Preferably, the pore creating material includes one or more groups in carbon black, sesbania powder, carboxymethyl cellulose and higher alcohols It closes；
Preferably, the aqueous solution of the basic active metal component includes wet chemical.
7. preparation method according to claim 5, it is characterised in that：In step 1, dry temperature is 100-120 DEG C, the dry time is 8-15h；The temperature of roasting is 490-630 DEG C, and the time of roasting is 4-8h；
Preferably, in step 2, the time of dipping is 5-10h；Dry temperature is 90-120 DEG C, and the dry time is 8- 13h；The temperature of roasting is 490-630 DEG C, and the time of roasting is 4-8h.
8. a kind of method of the depth dechlorination of ionic liquid allcylation oil comprising following steps：
Using fixed bed reactors, the fixed bed reactors include at least two and are connected；By the fixed bed reactors The adsorbent of any one of claim 1-4 load basic active components is loaded on middle bed；
Ionic liquid allcylation oil is passed through progress dechlorination processing in first fixed bed reactors, the ionic liquid after adsorption penetration Body alkylate oil is passed through again into another fixed bed reactors being connected with first fixed bed reactors into traveling one Walk dechlorination processing；
Preferably, this method further includes the steps that carrying out following regeneration to adsorbent：
Adsorbent reactivation of the vapor to load basic active component is passed through into the fixed bed reactors of adsorption saturation, regeneration is completed Stop being passed through vapor afterwards, and processing is dried to the adsorbent for loading basic active component using nitrogen, to be regenerated The adsorbent of load basic active component afterwards.
9. the method for depth dechlorination according to claim 8, which is characterized in that carry out absorption dechlorination condition be：It is fixed Temperature in bed reactor is 0-50 DEG C, pressure 0.5-2.0MPa；The air speed of ionic liquid allcylation oil is 0.25-4h-1。
10. the method for depth dechlorination according to claim 8, which is characterized in that the condition for carrying out adsorbent reactivation is：Gu Temperature in fixed bed reactor is 100-180 DEG C, pressure 0.1-0.5MPa；The air speed of vapor is 30-1000h-1。
CN201810379910.3A 2018-04-25 2018-04-25 Adsorbent loaded with alkali active component, preparation method thereof and deep dechlorination method Active CN108636348B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810379910.3A CN108636348B (en) 2018-04-25 2018-04-25 Adsorbent loaded with alkali active component, preparation method thereof and deep dechlorination method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810379910.3A CN108636348B (en) 2018-04-25 2018-04-25 Adsorbent loaded with alkali active component, preparation method thereof and deep dechlorination method

Publications (2)

Publication Number Publication Date
CN108636348A true CN108636348A (en) 2018-10-12
CN108636348B CN108636348B (en) 2020-04-24

Family

ID=63747740

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810379910.3A Active CN108636348B (en) 2018-04-25 2018-04-25 Adsorbent loaded with alkali active component, preparation method thereof and deep dechlorination method

Country Status (1)

Country Link
CN (1) CN108636348B (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109876768A (en) * 2019-04-04 2019-06-14 东营科尔特新材料有限公司 The method of dechlorination adsorbent and preparation method and compound ion liquid alkylate oil dechlorination
CN111097368A (en) * 2018-10-29 2020-05-05 中国石油化工股份有限公司 Adsorbing material and preparation method and application thereof
CN111171865A (en) * 2020-02-06 2020-05-19 中国石油大学(北京) Dechlorination method of waste plastic pyrolysis oil
CN111495387A (en) * 2020-02-25 2020-08-07 北京弗莱明科技有限公司 Chloropyridine hydrodechlorination catalyst and preparation method and application thereof
CN111514849A (en) * 2020-04-26 2020-08-11 东营科尔特新材料有限公司 Dechlorination adsorbent, preparation method and regeneration method thereof and application of dechlorination adsorbent to organic chlorine
CN112844306A (en) * 2020-12-23 2021-05-28 沈阳三聚凯特催化剂有限公司 Dechlorinating agent and preparation method and application thereof
CN113736507A (en) * 2020-05-27 2021-12-03 中国石油天然气股份有限公司 Liquid-phase dechlorinating agent, preparation method and application thereof
CN113952945A (en) * 2021-10-15 2022-01-21 沈阳三聚凯特催化剂有限公司 Dechlorinating agent and preparation method and application thereof
CN114425294A (en) * 2020-09-29 2022-05-03 中国石油化工股份有限公司 Supported adsorbent and preparation method and application thereof
CN115608407A (en) * 2022-10-13 2023-01-17 西安向阳航天材料股份有限公司 Preparation method of alkylate dechlorinating agent carrier
CN115646472A (en) * 2022-10-27 2023-01-31 山东亮剑环保新材料有限公司 High-efficiency carbon dioxide adsorbent and production method thereof
CN116272931A (en) * 2023-04-11 2023-06-23 北京铝能清新环境技术有限公司 Method and device for regenerating and treating waste dechlorinating agent of blast furnace gas

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104689787A (en) * 2013-12-09 2015-06-10 东营科尔特化工科技有限公司 Liquefied petroleum gas dechlorination adsorbent and application method thereof
CN204918487U (en) * 2015-08-13 2015-12-30 山东德阳化工有限公司 Alkylate dechlorination equipment
CN105601460A (en) * 2015-12-21 2016-05-25 中国石油大学(北京) Refining method of alkylation feedstock

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104689787A (en) * 2013-12-09 2015-06-10 东营科尔特化工科技有限公司 Liquefied petroleum gas dechlorination adsorbent and application method thereof
CN204918487U (en) * 2015-08-13 2015-12-30 山东德阳化工有限公司 Alkylate dechlorination equipment
CN105601460A (en) * 2015-12-21 2016-05-25 中国石油大学(北京) Refining method of alkylation feedstock

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KAZUYUKI CHIHARA ET AL.: "Molecular Simulation for Adsorption of Chlorinated Hydrocarbon in Zeolites", 《KOREAN J. CHEM. ENG.》 *

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111097368A (en) * 2018-10-29 2020-05-05 中国石油化工股份有限公司 Adsorbing material and preparation method and application thereof
CN109876768A (en) * 2019-04-04 2019-06-14 东营科尔特新材料有限公司 The method of dechlorination adsorbent and preparation method and compound ion liquid alkylate oil dechlorination
CN111171865B (en) * 2020-02-06 2022-04-01 中国石油大学(北京) Dechlorination method of waste plastic pyrolysis oil
CN111171865A (en) * 2020-02-06 2020-05-19 中国石油大学(北京) Dechlorination method of waste plastic pyrolysis oil
CN111495387A (en) * 2020-02-25 2020-08-07 北京弗莱明科技有限公司 Chloropyridine hydrodechlorination catalyst and preparation method and application thereof
CN111514849A (en) * 2020-04-26 2020-08-11 东营科尔特新材料有限公司 Dechlorination adsorbent, preparation method and regeneration method thereof and application of dechlorination adsorbent to organic chlorine
CN111514849B (en) * 2020-04-26 2023-10-31 东营科尔特新材料有限公司 Dechlorination adsorbent, preparation method thereof, regeneration method thereof and application of dechlorination adsorbent in removal of organic chlorine
CN113736507A (en) * 2020-05-27 2021-12-03 中国石油天然气股份有限公司 Liquid-phase dechlorinating agent, preparation method and application thereof
CN113736507B (en) * 2020-05-27 2023-08-22 中国石油天然气股份有限公司 Liquid phase dechlorinating agent, preparation method and application thereof
CN114425294A (en) * 2020-09-29 2022-05-03 中国石油化工股份有限公司 Supported adsorbent and preparation method and application thereof
CN114425294B (en) * 2020-09-29 2024-02-13 中国石油化工股份有限公司 Supported adsorbent and preparation method and application thereof
CN112844306A (en) * 2020-12-23 2021-05-28 沈阳三聚凯特催化剂有限公司 Dechlorinating agent and preparation method and application thereof
CN113952945A (en) * 2021-10-15 2022-01-21 沈阳三聚凯特催化剂有限公司 Dechlorinating agent and preparation method and application thereof
CN113952945B (en) * 2021-10-15 2024-05-17 沈阳三聚凯特催化剂有限公司 Dechlorination agent and preparation method and application thereof
CN115608407A (en) * 2022-10-13 2023-01-17 西安向阳航天材料股份有限公司 Preparation method of alkylate dechlorinating agent carrier
CN115646472A (en) * 2022-10-27 2023-01-31 山东亮剑环保新材料有限公司 High-efficiency carbon dioxide adsorbent and production method thereof
CN116272931A (en) * 2023-04-11 2023-06-23 北京铝能清新环境技术有限公司 Method and device for regenerating and treating waste dechlorinating agent of blast furnace gas

Also Published As

Publication number Publication date
CN108636348B (en) 2020-04-24

Similar Documents

Publication Publication Date Title
CN108636348A (en) The method for loading adsorbent of basic active component and preparation method thereof and depth dechlorination
CN104492383B (en) A kind of metal organic frame adsorbent and its preparation method and application
CN106118717B (en) One kind is with Ag2O/SiO2Composite aerogel is the method that adsorbent removes thiophene sulphur in fuel oil
Okunev et al. Sorption of carbon dioxide from wet gases by K2CO3-in-porous matrix: influence of the matrix nature
RU2517639C2 (en) Adsorbent, method for production thereof and method of removing sulphur from cracked petrol or diesel fuel
CN1680001A (en) Hydrocarbon separation method
DE2356551A1 (en) PROCESS FOR THE REMOVAL OF WATER AND SULFUR FROM HYDROCARBONS
CN107876005B (en) Adsorbent for removing chlorinated pollutants and preparation method and application thereof
CN104588075B (en) Preparation method for alkylation catalyst
CN104941639B (en) A kind of selective hydrogenation catalyst and its preparation method and application
CN101323794B (en) Spherical active carbon fuel oil adsorption desulfurizing agent and preparation thereof
CN1594505A (en) Process for adsorption desulfurization of gasoline
BR112017000225B1 (en) ALKILLATION PROCESS WITH THE ASSISTANCE OF A CATALYST THAT UNDERSTANDS ZEOLITES WHICH CONTAIN TERRIBLE TERRIES RICH IN CEREMONY AND A METAL OF HYDROGENATION
CN103495435A (en) Catalyst for removing olefins in reformate and preparation method of catalyst
CN110872527B (en) C4～C6Light paraffin isomerization method
CN107573964A (en) A kind of n-alkane low temperature isomerization method and device
CN106278781A (en) A kind of light paraffins isomerization method
CN104549139A (en) Cu-containing molecular sieve adsorbent and preparation method thereof
CN104549469B (en) Reproducible polycyclic aromatic hydrocarbon is converted into catalyst of mononuclear aromatics and preparation method thereof
CN106833738B (en) A kind of raising C5/C6The method of alkane octane number
WO2023151561A1 (en) Adsorbent for separating ethylbenzene from c8 aromatic hydrocarbons and preparation method therefor
CN105080476B (en) Cupric and halogenic molecule sieve adsorbant and preparation method thereof
CN109876768A (en) The method of dechlorination adsorbent and preparation method and compound ion liquid alkylate oil dechlorination
CN113083223B (en) Adsorption dehydrating agent for electronic grade gas and preparation method thereof
CN108070415A (en) A kind of liquefied petroleum gas desulfurizing method by adsorption

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