CN110876922A - Naphtha dechlorination adsorbent and preparation method and application thereof - Google Patents
Naphtha dechlorination adsorbent and preparation method and application thereof Download PDFInfo
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- CN110876922A CN110876922A CN201811035584.0A CN201811035584A CN110876922A CN 110876922 A CN110876922 A CN 110876922A CN 201811035584 A CN201811035584 A CN 201811035584A CN 110876922 A CN110876922 A CN 110876922A
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- molecular sieve
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 87
- 238000006298 dechlorination reaction Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000002808 molecular sieve Substances 0.000 claims abstract description 61
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 61
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 30
- 239000000460 chlorine Substances 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 23
- 238000001179 sorption measurement Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 10
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000000463 material Substances 0.000 claims 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 238000004898 kneading Methods 0.000 abstract description 3
- 238000010924 continuous production Methods 0.000 abstract description 2
- 241000219782 Sesbania Species 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 230000036314 physical performance Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910003112 MgO-Al2O3 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000382 dechlorinating effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—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 physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- 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
- B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 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
-
- 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
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the technical field of petrochemical industry, and particularly relates to a naphtha dechlorination adsorbent and a preparation method and application thereof. The naphtha dechlorination adsorbent is prepared from the following raw materials in percentage by weight: 2.0-10.0% of 5A molecular sieve; 5.0 to 20.0 percent of NaY molecular sieve; 10.0 to 40.0 percent of 10X molecular sieve; 5.0 to 20.0 percent of 13X molecular sieve; the balance is quick-release powder. The adsorbent prepared by the invention has excellent adsorption performance on organic chlorine in naphtha. The preparation method is safe, environment-friendly and simple, and the active components are uniformly dispersed and are not easy to run off by adopting a kneading method. The adsorbent is suitable for a fixed bed continuous process, and has the operating pressure of 0.1-0.5 MPa and the airspeed of 0.5h at the temperature of 40-60 DEG C‑1～3h‑1Can adsorb organic chlorine in naphtha to 1ppm or less.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, and particularly relates to a naphtha dechlorination adsorbent and a preparation method and application thereof.
Background
As crude oil is heavy, the difficulty of crude oil recovery is increasing. In order to improve the recovery efficiency, a plurality of organic chlorine chemical additives are used in the oil extraction process, so that the content of organic chlorine in crude oil is higher, the organic chlorine is brought into naphtha in the crude oil distillation process, the naphtha is used as an important chemical raw material, and the content of the organic chlorine is strictly controlled in order to prevent the organic chlorine from corroding or having other negative effects on a processing device, so that the research on the technology for scientifically and effectively removing the organic chlorine from the naphtha has important practical significance.
Research on non-hydrogenation adsorption dechlorination of literature straight run naphtha, ZSM-5 molecular sieve with larger specific surface area and gamma-Al2O3Respectively loading active components CuO and MgO on a carrier by an isometric kneading method to prepare CuO/ZSM-5, MgO/ZSM-5 and CuO/gamma-Al as carriers2O3、MgO/γ-Al2O34 adsorbents, when the CuO loading is 12% (w), the mass ratio of the adsorbent to the straight run naphtha is 1: 15. under the optimal adsorption condition with the adsorption time of 20min, CuO/gamma-Al2O3The adsorption effect is best, the removal rate of the chloride reaches 59.93 percent, the dechlorination efficiency is low, and the method is not suitable for deep dechlorination.
Patent US3864243 discloses a method for removing chlorides and other impurities from hydrocarbons using a zeolite molecular sieve, which is carried out by an adsorption method using a 13X or 10X zeolite molecular sieve at normal temperature and pressure, but has a low adsorption capacity.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a naphtha dechlorination adsorbent which has excellent adsorption performance on organic chlorine in naphtha; the invention also provides a preparation method and application thereof, and the preparation method is safe, environment-friendly and simple.
The naphtha dechlorination adsorbent is prepared from the following raw materials in percentage by weight:
preferably, the naphtha dechlorination adsorbent is prepared from the following raw materials in percentage by weight:
the adsorbent is suitable for adsorbing and dechlorinating naphtha.
The preparation method of the naphtha dechlorination adsorbent comprises the following steps:
uniformly mixing the 5A molecular sieve, the NaY molecular sieve, the 10X molecular sieve, the 13X molecular sieve, the quick-release powder and the adhesive, adding nitric acid, extruding into strips, forming, drying, roasting, and naturally cooling to obtain the naphtha dechlorination adsorbent.
The adhesive is sesbania powder, and the dosage of the adhesive is 2-5% of the total mass of the 5A molecular sieve, the NaY molecular sieve, the 10X molecular sieve, the 13X molecular sieve and the quick-release powder.
The concentration of the nitric acid is 3-10%, and the dosage of the nitric acid is 20-40% of the total mass of the 5A molecular sieve, the NaY molecular sieve, the 10X molecular sieve, the 13X molecular sieve and the quick-release powder.
The drying temperature is 105-120 ℃, and the drying time is 1-3 hours.
Preferably, the drying temperature is 120 ℃ and the drying time is 2 hours.
The roasting temperature is 450-600 ℃, and the roasting time is 3-8 hours.
The application of the naphtha dechlorination adsorbent is as follows:
the naphtha dechlorination adsorbent is arranged in an adsorbent bed layer in the fixed bed reactor, and naphtha containing organic chlorine is adsorbed through the adsorbent bed layer.
The adsorption is carried out under the operating pressure of 0.1-0.5 MPa and at the operating temperature of 40-60 ℃.
The space velocity of the naphtha containing the organic chlorine passing through the adsorbent bed is 0.5h-1～3h-1。
The technical indexes of the naphtha dechlorination adsorbent prepared by the invention are as follows:
in conclusion, the beneficial effects of the invention are as follows:
1. the adsorbent prepared by the invention has excellent adsorption performance on organic chlorine in naphtha. The adsorption dechlorination is a cheap and effective new technology, and has the advantages of low investment, mild conditions, small equipment space, low cost and suitability for deep dechlorination.
2. The preparation method disclosed by the invention is safe, environment-friendly, simple and convenient, and the active components are uniformly dispersed and are not easy to run off by adopting a kneading method.
3. The adsorbent is suitable for a fixed bed continuous process, and has the operating pressure of 0.1-0.5 MPa and the airspeed of 0.5h at the temperature of 40-60 DEG C-1～3h-1Can adsorb organic chlorine in naphtha to 1ppm or less.
Drawings
FIG. 1 is a schematic view of the structure of a fixed bed evaluation apparatus of the present invention;
in the figure: 1. the device comprises a raw material tank, 2 a raw material metering pump, 3 a fixed bed reactor, 4 a water bath inlet, 5a water bath outlet, 6 a sampling port, 7 a reaction pressure controller, 8 a condenser, 9 a collecting tank, 10 a vent, 11 a thermocouple tube.
Detailed Description
The present invention will be further described with reference to the following examples.
The raw materials used in the examples were all commercially available except as specifically indicated.
Example 1
The preparation method of the naphtha dechlorination adsorbent A comprises the following steps:
3g of 5A molecular sieve, 7g of NaY molecular sieve, 40g of 10X molecular sieve, 20g of 13X molecular sieve, 30g of quick-release powder and 3g of sesbania powder are uniformly mixed, 30g of dilute nitric acid with the mass concentration of 5% is added, and then the mixture is extruded into strips and formed, wherein the diameter is phi 1.8-2.5 mm. Drying for 2 hours at 120 ℃, then roasting for 3 hours at 450 ℃ in a muffle furnace, and naturally cooling to obtain the adsorbent, namely the naphtha dechlorination adsorbent A.
The concrete conditions of the mass percentage of each component are shown in table 1, and the physical performance indexes of the adsorbent, such as pore volume, specific surface and strength, are shown in table 2.
Crushing the obtained adsorbent A to 20-40 meshes, putting 40ml of the adsorbent A into a fixed bed reactor with phi of 25 multiplied by 2.5mm, taking naphtha containing about 30ppm of organic chlorine, and performing reaction at the temperature of 40 ℃, the operating pressure of 0.2MPa and the liquid space velocity (LHSV) of 2h-1The product was sampled and analyzed by the adsorbent bed under the conditions of (1). The results show that no organic chlorine was detected in the product naphtha.
Example 2
The preparation method of the naphtha dechlorination adsorbent B comprises the following steps:
5g of 5A molecular sieve, 5g of NaY molecular sieve, 30g of 10X molecular sieve, 10g of 13X molecular sieve, 50g of quick-release powder and 4g of sesbania powder are uniformly mixed, 20g of dilute nitric acid with the mass concentration of 5% is added, and then the mixture is extruded into strips and formed, wherein the diameter is phi 1.8-2.5 mm. Drying for 2 hours at 120 ℃, then roasting for 5 hours in a muffle furnace at 500 ℃, and naturally cooling to obtain the adsorbent, namely the naphtha dechlorination adsorbent.
The concrete conditions of the mass percentage content of each component are shown in table 1, and the physical performance indexes of the adsorbent such as pore volume, specific surface and strength are shown in table 2.
Pulverizing the obtained adsorbent B to 20-40 mesh, placing 40ml in a fixed bed reactor with phi of 25X 2.5mm, and taking the adsorbentNaphtha with about 30ppm of chlorine at a temperature of 50 ℃, an operating pressure of 0.3MPa and a liquid space velocity (LHSV) of 1h-1The product was sampled and analyzed by the adsorbent bed under the conditions of (1). The results show that no organic chlorine was detected in the product naphtha.
Example 3
The preparation method of the naphtha dechlorination adsorbent C comprises the following steps:
uniformly mixing 10g of 5A molecular sieve, 10g of NaY molecular sieve, 20g of 10X molecular sieve, 20g of 13X molecular sieve, 40g of quick-release powder and 5g of sesbania powder, adding 40g of dilute nitric acid with the mass concentration of 3%, extruding into strips, and forming, wherein the diameter is phi 1.8-2.5 mm. Drying for 2 hours at 120 ℃, then roasting for 3 hours at 550 ℃ in a muffle furnace, and naturally cooling to obtain the adsorbent, namely the naphtha dechlorination adsorbent.
The concrete conditions of the mass percentage content of each component are shown in table 1, and the physical performance indexes of the adsorbent such as pore volume, specific surface and strength are shown in table 2.
Crushing the obtained adsorbent C to 20-40 meshes, putting 40ml of the adsorbent C into a fixed bed reactor with phi of 25 multiplied by 2.5mm, taking naphtha containing about 30ppm of organic chlorine, and performing reaction at the temperature of 40 ℃, the operating pressure of 0.1MPa and the liquid space velocity (LHSV) of 3h-1The product was sampled and analyzed by the adsorbent bed under the conditions of (1). The results show that no organic chlorine was detected in the product naphtha.
Example 4
The preparation method of the naphtha dechlorination adsorbent D comprises the following steps:
8g of 5A molecular sieve, 12g of NaY molecular sieve, 20g of 10X molecular sieve, 15g of 13X molecular sieve, 45g of quick-release powder and 5g of sesbania powder are uniformly mixed, 30g of dilute nitric acid with the mass concentration of 8% is added, and then the mixture is extruded into strips and formed, wherein the diameter is phi 1.8-2.5 mm. Drying for 2 hours at 120 ℃, then roasting for 8 hours at 450 ℃ in a muffle furnace, and naturally cooling to obtain the adsorbent, namely the naphtha dechlorination adsorbent.
The concrete conditions of the mass percentage content of each component are shown in table 1, and the physical performance indexes of the adsorbent such as pore volume, specific surface and strength are shown in table 2.
The obtained adsorbent D is crushed to 20-40 meshes,placing 40ml into a fixed bed reactor with diameter of 25 × 2.5mm, taking naphtha containing about 30ppm of organic chlorine, and maintaining the temperature at 50 deg.C, the operating pressure at 0.4MPa, and the liquid space velocity (LHSV) at 0.5h-1The product was sampled and analyzed by the adsorbent bed under the conditions of (1). The results show that no organic chlorine was detected in the product naphtha.
Example 5
The preparation method of the naphtha dechlorination adsorbent E comprises the following steps:
8g of 5A molecular sieve, 12g of NaY molecular sieve, 25g of 10X molecular sieve, 15g of 13X molecular sieve, 40g of quick-release powder and 5g of sesbania powder are uniformly mixed, 30g of dilute nitric acid with the mass concentration of 10% is added, and then the mixture is extruded into strips and formed, wherein the diameter is phi 1.8-2.5 mm. Drying for 2 hours at 120 ℃, then roasting for 5 hours in a muffle furnace at 500 ℃, and naturally cooling to obtain the adsorbent, namely the naphtha dechlorination adsorbent.
The concrete conditions of the mass percentage content of each component are shown in table 1, and the physical performance indexes of the adsorbent such as pore volume, specific surface and strength are shown in table 2.
Crushing the obtained adsorbent E to 20-40 meshes, putting 40ml of the adsorbent E into a fixed bed reactor with phi of 25 multiplied by 2.5mm, taking naphtha containing about 30ppm of organic chlorine, and sampling and analyzing products through an adsorbent bed layer under the conditions that the temperature is 60 ℃, the operating pressure is 0.2MPa and the liquid space velocity (LHSV) is 3h < -1 >. The results show that no organic chlorine was detected in the product naphtha.
Example 6
The preparation method of the naphtha dechlorination adsorbent F comprises the following steps:
3g of 5A molecular sieve, 17g of NaY molecular sieve, 10g of 10X molecular sieve, 20g of 13X molecular sieve, 50g of quick-release powder and 3g of sesbania powder are uniformly mixed, 30g of dilute nitric acid with the mass concentration of 5% is added, and then the mixture is extruded into strips and formed, wherein the diameter is phi 1.8-2.5 mm. Drying for 2 hours at 120 ℃, then roasting for 5 hours at 550 ℃ in a muffle furnace, and naturally cooling to obtain the adsorbent, namely the naphtha dechlorination adsorbent.
The concrete conditions of the mass percentage content of each component are shown in table 1, and the physical performance indexes of the adsorbent such as pore volume, specific surface and strength are shown in table 2.
Crushing the obtained adsorbent F to 20-40 meshes, putting 40ml of the adsorbent in a fixed bed reactor with phi of 25 multiplied by 2.5mm, taking naphtha containing about 30ppm of organic chlorine, and performing reaction at the temperature of 50 ℃, the operating pressure of 0.2MPa and the liquid space velocity (LHSV) of 1h-1The product was sampled and analyzed by the adsorbent bed under the conditions of (1). The results show that no organic chlorine was detected in the product naphtha.
Example 7
The preparation method of the naphtha dechlorination adsorbent G comprises the following steps:
uniformly mixing 10g of 5A molecular sieve, 17g of NaY molecular sieve, 23g of 10X molecular sieve, 20g of 13X molecular sieve, 30g of quick-release powder and 3g of sesbania powder, adding 40g of dilute nitric acid with the mass concentration of 5%, extruding into strips and forming, wherein the diameter is phi 1.8-2.5 mm. Drying for 2 hours at 120 ℃, then roasting for 4 hours at 500 ℃ in a muffle furnace, and naturally cooling to obtain the adsorbent, namely the naphtha dechlorination adsorbent.
The concrete conditions of the mass percentage content of each component are shown in table 1, and the physical performance indexes of the adsorbent such as pore volume, specific surface and strength are shown in table 2.
Pulverizing the obtained adsorbent G to 20-40 mesh, placing 40ml into a fixed bed reactor with phi of 25 x 2.5mm, taking naphtha containing about 30ppm of organic chlorine, and performing Liquid Hourly Space Velocity (LHSV) of 2h at 60 deg.C and 0.4MPa-1The product was sampled and analyzed by the adsorbent bed under the conditions of (1). The results show that no organic chlorine was detected in the product naphtha.
Comparative example
The adsorbent is prepared by adopting the composition described in patent US3864243 and adopting the adsorbent preparation method disclosed by the invention, and specifically, 40g of zeolite molecular sieve and 60g of 13X molecular sieve are uniformly mixed, 30g of dilute nitric acid with the mass concentration of 5% is added, and then the mixture is extruded into strips and formed, wherein the diameter is phi 1.8-2.5 mm. Drying for 2 hours at 120 ℃, then roasting for 5 hours at 550 ℃ in a muffle furnace, and naturally cooling to obtain the adsorbent, namely the naphtha dechlorination adsorbent.
Pulverizing the obtained adsorbent to 20-40 mesh, placing 40ml into a fixed bed reactor with phi 25 × 2.5mm, taking naphtha containing about 30ppm of organic chlorine, and heating at a temperature of50 ℃, the operating pressure of 0.2MPa and the liquid space velocity (LHSV) of 1h-1The product was sampled and analyzed by the adsorbent bed under the conditions of (1). The results show that the organochlorine content in the product naphtha was 19 ppm.
The dechlorination effect of the adsorbent prepared by adopting the comparative example is obviously inferior to that of the embodiment. TABLE 1 adsorbent composition
TABLE 2 physical Properties of the adsorbents
| Examples | Sorbent numbering | Pore volume ml g-1 | Specific surface m2·g-1 | Strength N/cm |
| 1 | A | 0.56 | 550 | 89 |
| 2 | B | 0.66 | 610 | 71 |
| 3 | C | 0.57 | 497 | 77 |
| 4 | D | 0.57 | 570 | 90 |
| 5 | E | 0.49 | 575 | 91 |
| 6 | F | 0.54 | 680 | 83 |
| 7 | G | 0.59 | 767 | 75 |
Claims (10)
1. A naphtha dechlorination adsorbent is characterized in that: the material is prepared from the following raw materials in percentage by weight:
2. the naphtha dechlorination adsorbent of claim 1, characterized in that: the material is prepared from the following raw materials in percentage by weight:
3. a method for preparing the naphtha dechlorination adsorbent according to claim 1 or 2, which is characterized by comprising the following steps: the method comprises the following steps:
uniformly mixing the 5A molecular sieve, the NaY molecular sieve, the 10X molecular sieve, the 13X molecular sieve, the quick-release powder and the adhesive, adding nitric acid, extruding into strips, forming, drying, roasting, and naturally cooling to obtain the naphtha dechlorination adsorbent.
4. The production method according to claim 3, characterized in that: the adhesive is sesbania powder, and the dosage of the adhesive is 2-5% of the total mass of the 5A molecular sieve, the NaY molecular sieve, the 10X molecular sieve, the 13X molecular sieve and the quick-release powder.
5. The production method according to claim 3, characterized in that: the concentration of the nitric acid is 3-10%, and the dosage of the nitric acid is 20-40% of the total mass of the 5A molecular sieve, the NaY molecular sieve, the 10X molecular sieve, the 13X molecular sieve and the quick-release powder.
6. The production method according to claim 3, characterized in that: the drying temperature is 105-120 ℃, and the drying time is 1-3 hours.
7. The production method according to claim 3, characterized in that: the roasting temperature is 450-600 ℃, and the roasting time is 3-8 hours.
8. Use of the naphtha dechlorination adsorbent of claim 1 or 2, characterized in that: the naphtha dechlorination adsorbent is arranged in an adsorbent bed layer in the fixed bed reactor, and naphtha containing organic chlorine is adsorbed through the adsorbent bed layer.
9. Use according to claim 8, characterized in that: the adsorption is carried out under the operating pressure of 0.1-0.5 MPa and at the operating temperature of 40-60 ℃.
10. Use according to claim 8, characterized in that: the space velocity of the naphtha containing the organic chlorine passing through the adsorbent bed is 0.5h-1～3h-1。
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