CN111974340A - Desulfurization adsorbent, preparation method thereof and method for deeply desulfurizing hydrocarbon - Google Patents

Desulfurization adsorbent, preparation method thereof and method for deeply desulfurizing hydrocarbon Download PDF

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CN111974340A
CN111974340A CN202010877401.0A CN202010877401A CN111974340A CN 111974340 A CN111974340 A CN 111974340A CN 202010877401 A CN202010877401 A CN 202010877401A CN 111974340 A CN111974340 A CN 111974340A
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molecular sieve
desulfurization
pore
drying
barium
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CN111974340B (en
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周广林
李芹
姜伟丽
王晓胜
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China University of Petroleum Beijing
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • 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
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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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4012—Pressure
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

The invention provides a desulfurization adsorbent, a preparation method thereof and a method for deeply desulfurizing tetraalkyl hydrocarbons. The desulfurization adsorbent comprises the following components in percentage by weight of 100 wt%: 60 to 85 weight percent of micro-mesoporous molecular sieve carrier, 2 to 16 weight percent of copper oxide, 1 to 18 weight percent of nickel oxide, 0.2 to 5.0 weight percent of barium oxide and 0.2 to 5.0 weight percent of calcium oxide. The desulfurization adsorbent has high adsorption desulfurization activity, strong selectivity and high sulfur capacity; the catalyst is used for the deep desulfurization of the tetrakakyl hydrocarbon, has mild operation conditions, flexible adaptability to the tetrakakyl hydrocarbon raw material and high desulfurization efficiency.

Description

Desulfurization adsorbent, preparation method thereof and method for deeply desulfurizing hydrocarbon
Technical Field
The invention belongs to the technical field of desulfurization adsorbents, and particularly relates to a desulfurization adsorbent, a preparation method thereof and a method for deep desulfurization of tetraalkyl carbon.
Background
Isobutene is used as an important basic organic chemical raw material, has wide application and is increasingly demanded. Isobutane dehydrogenation technology is one of the effective methods for increasing the yield of isobutene. The composition of the tetrakacarbon as one of the starting materials for dehydrogenation is relatively complex. The tetrakaines often contain sulfur-containing compounds, oxygen-containing compounds, and nitrogen-containing compounds in varying amounts due to differences in sources, production processes, and transportation processes. The sulfur-containing compound in the impurities has strong polarity, and the byproduct isobutane contains impurities such as sulfur dioxide and the like, so that the downstream tetraalkyl hydrocarbon dehydrogenation catalyst is poisoned and inactivated. Therefore, in order to fully and reasonably utilize the tetrakam, the tetrakam must be subjected to deep desulfurization, and the deep desulfurization of the tetrakam is gradually key to further processing and utilization of the tetrakam.
At present, the method for removing sulfides in the carbon-tetralkyl hydrocarbon mainly comprises three methods, namely hydrogenation, alkali washing and adsorption. The hydrogenation method needs a special catalyst, and because part of sulfides are difficult to hydrogenate, deep hydrogenation is needed for removing the sulfides by hydrogenation, so that the energy consumption is high and the economical efficiency is poor. The alkaline washing method mainly uses alkali as an absorbent, has high sulfide removal efficiency and easy operation and control, but has the problem of post-treatment of waste alkali liquor, and the alkaline washing is difficult to achieve the effect of deeply removing sulfides. The adsorption method has simple process, low energy consumption, no corrosion and no pollution, and particularly, the purification depth of the adsorption is far higher than the purification process of hydrogenation and alkali washing when the content of sulfide is very low, so the adsorption method is more suitable for deep removal of the raw material sulfide.
However, the existing desulfurization adsorbent has low desulfurization efficiency, poor desulfurization precision and low sulfur capacity, and cannot meet the requirement of deep desulfurization of the tetracarbon.
Disclosure of Invention
Based on the problems existing in the prior art, the first objective of the present invention is to provide a desulfurization adsorbent, which uses a step pore molecular sieve containing micropores and mesopores as a carrier, and is obtained by doping barium and calcium and loading copper and nickel; the second purpose of the invention is to provide a preparation method of the desulfurization adsorbent; the third purpose of the invention is to provide a method for deeply desulfurizing the tetrakam by using the desulfurizing adsorbent.
The purpose of the invention is realized by the following technical scheme:
in one aspect, the present invention provides a desulfurization adsorbent, wherein the desulfurization adsorbent comprises, by weight, 100 wt%:
Figure BDA0002653024560000021
in the desulfurization adsorbent, the barium and calcium elements are doped, so that the acidity of the surface of the carrier can be adjusted, the dispersion degree and the adhesiveness of the active components copper and nickel on the carrier are improved, the loss of the active components is inhibited, and the problem of activity reduction of the adsorbent caused by the loss of the active components is effectively solved.
In the above desulfurization adsorbent, preferably, the desulfurization adsorbent comprises, in 100 wt% by weight:
Figure BDA0002653024560000022
in the desulfurization adsorbent, preferably, the micro mesoporous molecular sieve carrier has a pore size distribution of 1-15 nm, a total pore volume of 0.3-0.5 ml/g, and a specific surface area of 500-550 m2/g；
Wherein the pore diameter distribution of the micropores is 1-2 nm, and the pore volume of the micropores accounts for 40% -80% of the total pore volume; the mesoporous aperture distribution is 8-15 nm, and the mesoporous volume accounts for 20-60% of the total pore volume.
According to the micro-mesoporous molecular sieve carrier, reagents such as a dispersing agent, a chelating agent and the like do not need to be added, the preparation cost is greatly reduced, the added pore-expanding agent is easy to obtain, and the preparation process is easy to popularize. The carrier of the micro-mesoporous has two advantages, namely, the specific surface area is higher, and the load of the metal active component is more uniform; secondly, the mass transfer resistance is small, the diffusion of the sulfide is fast during the adsorption, and the adsorption effect is good.
On the other hand, the invention also provides a preparation method of the desulfurization adsorbent, which comprises the following steps:
mixing soluble barium salt and soluble calcium salt, adding water to prepare a first impregnation solution, impregnating a micro mesoporous molecular sieve carrier in the first impregnation solution, drying after impregnation, and roasting to obtain a barium-calcium modified carrier;
and mixing soluble copper salt and soluble nickel salt, adding water to prepare a second impregnation solution, impregnating the barium-calcium modified carrier in the second impregnation solution, drying after impregnation, and roasting to obtain the desulfurization adsorbent.
In the preparation method, the dosage of soluble barium salt, soluble calcium salt, soluble copper salt, soluble nickel salt, micro-mesoporous molecular sieve carrier and water is properly adjusted according to actual operation so as to meet the requirement that the content of the micro-mesoporous molecular sieve carrier, copper oxide, nickel oxide, barium oxide and calcium oxide in the finally roasted desulfurization adsorbent meets the proportion range.
In the above preparation method, preferably, the soluble barium salt includes barium nitrate and/or barium chloride; the soluble calcium salt comprises calcium nitrate and/or calcium chloride, etc.; the soluble copper salt comprises copper nitrate and/or copper chloride and the like; the soluble nickel salt comprises nickel nitrate and/or nickel chloride and the like.
In the above preparation method, preferably, the soluble barium salt, the soluble calcium salt, the soluble copper salt and the soluble nickel salt are nitrates thereof.
In the preparation method, preferably, the first impregnation liquid is impregnated at normal temperature for 12-20 hours; drying at 90-140 ℃ for 4-10 h after dipping; the roasting temperature after drying is 350-550 ℃, and the roasting time is 4-9 h.
In the preparation method, preferably, the temperature of immersion in the second immersion liquid is normal temperature, and the immersion time is 12-20 hours; drying at 90-140 ℃ for 4-10 h after dipping; the roasting temperature after drying is 350-550 ℃, and the roasting time is 4-9 h.
In the above preparation method, preferably, the preparation method of the mesoporous molecular sieve support comprises:
adding organic acid and/or inorganic acid into the aluminum sol to obtain an aluminum sol acid solution, and then dissolving the pore-expanding agent into the aluminum sol acid solution to obtain an aluminum sol acid solution containing the pore-expanding agent;
adding molecular sieve powder and carboxymethyl cellulose into a kneader, uniformly mixing, adding an aluminum sol acid solution containing a pore-expanding agent, and continuously kneading uniformly;
the molecular sieve carrier with the micro-mesoporous structure is obtained through extrusion, molding, drying and roasting.
In the above preparation method, preferably, the mass ratio of the pore-expanding agent to the aluminum sol is 1: (4-20); in the aluminum sol, the content of aluminum oxide is 20 wt% -25 wt%.
In the above preparation method, preferably, the pore-expanding agent may include polyvinyl alcohol or the like.
The polyvinyl alcohol is used as a pore-expanding agent, so that the molecular sieve carrier has good solubility and stability, a micropore and mesoporous structure can be generated more easily, a micro mesoporous structure with adjustable pore size distribution can be obtained, and the pore size distribution range is 1-15 nm.
In the above preparation method, preferably, the organic acid includes oxalic acid and/or citric acid; the inorganic acid includes nitric acid and/or hydrochloric acid, etc.
In the above preparation method, preferably, the molecular sieve powder comprises one or more of raw powder of NaY molecular sieve, raw powder of NaX molecular sieve, raw powder of ZSM-5 molecular sieve, raw powder of MCM-41 molecular sieve, and the like.
In the above preparation method, preferably, the amount of the organic acid and/or the inorganic acid is 2 wt% to 35 wt% of the pore-enlarging agent.
In the above preparation method, preferably, the mass ratio of the molecular sieve powder to the carboxymethyl cellulose is (10-30): 1.
in the above preparation method, preferably, the mass ratio of the pore-expanding agent to the molecular sieve powder is 1: (10-50).
In the preparation method, preferably, the drying temperature after extrusion molding is 90-140 ℃, and the drying time is 4-10 h; the roasting temperature after drying is 350-550 ℃, and the roasting time is 4-9 h.
In still another aspect, the present invention also provides a method for deep desulfurization of a tetraalkyl carbon, comprising the steps of:
adopting a fixed bed reactor, wherein the desulfurization adsorbent is filled in the fixed bed reactor;
and introducing the tetrakam into a fixed bed reactor for desulfurization treatment to obtain desulfurized tetrakam.
In the deep desulfurization method, preferably, in the desulfurization process, the reaction temperature is 0-80 ℃, the reaction pressure is 0.4-2.5 MPa, and the space velocity of the liquid volume of the tetracarbon is 0.2-5.0 h-1。
In the deep desulfurization method, preferably, in the desulfurization process, the reaction temperature is 10-70 ℃, the reaction pressure is 0.6-2.0 MPa, and the space velocity of the liquid volume of the tetracarbon is 0.5-4.0 h-1。
The desulfurization adsorbent has high adsorption desulfurization activity, strong selectivity and high sulfur capacity; the catalyst is used for the deep desulfurization of the tetrakakyl hydrocarbon, has mild operation conditions, flexible adaptability to the tetrakakyl hydrocarbon raw material and high desulfurization efficiency.
Drawings
Fig. 1 is a diagram illustrating a pore size distribution of a micro mesoporous molecular sieve carrier prepared in example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
The isobutane feed in the following examples was derived from the isobutane feed separated in the sulphuric acid alkylation unit and had the composition shown in table 1:
table 1:
components Content/w%
Propane 0.58
Isobutane 89.16
N-butane 9.63
C5+ 0.58
The analysis method adopts an ultraviolet fluorescence sulfur determinator to determine the sulfur content of the isobutane raw material obtained by separation of the alkylation device before and after desulfurization, and the sulfur dioxide content of the isobutane raw material before desulfurization is 280 mg/kg.
Example 1:
the embodiment provides a preparation method of a desulfurization adsorbent, which comprises the following steps:
weighing 240g of alumina sol containing 25% of alumina by using a beaker, adding 5.0g of oxalic acid into the alumina sol, uniformly mixing, and then adding the oxalic acid into the alumina sol to obtain an alumina sol oxalic acid solution; 15.0g of polyvinyl alcohol pore-expanding agent is weighed and added into the prepared alumina sol oxalic acid solution, and the mixture is uniformly stirred to obtain the alumina sol oxalic acid solution containing the pore-expanding agent.
300g of NaY molecular sieve raw powder and 13g of carboxymethyl cellulose are weighed and added into a kneader to be uniformly mixed, and then an aluminum sol oxalic acid solution containing a pore-expanding agent is added to be continuously kneaded uniformly.
Kneading and extruding the mixture into a cylindrical shape, drying the cylindrical shape for 8 hours at the temperature of 110 ℃, and roasting the cylindrical shape for 4 hours at the temperature of 550 ℃ to obtain the molecular sieve carrier M-1 with the micro-mesopores, wherein the specific surface area and the pore size distribution of the molecular sieve carrier are shown in Table 2. FIG. 1 is a pore size distribution diagram of the micro mesoporous molecular sieve carrier M-1.
As can be seen from FIG. 1, the mesoporous molecular sieve carrier M-1 prepared in this example has a relatively concentrated pore size distribution between the pore sizes of 2nm and 6-14 nm, which indicates that the prepared mesoporous molecular sieve carrier M-1 has a composite stepped pore structure.
Weighing 12.63g of barium nitrate and 31.24g of calcium nitrate tetrahydrate, adding the barium nitrate and the calcium nitrate tetrahydrate into 100ml of distilled water to prepare an auxiliary agent impregnation liquid, then impregnating 360g of a micro-mesoporous molecular sieve carrier M-1, impregnating at normal temperature for 20h, drying at 110 ℃ for 8h after impregnation, and roasting at 530 ℃ for 3h to obtain 374.8g of the barium calcium modified molecular sieve carrier.
Then 89.98g of copper nitrate trihydrate and 100.91g of nickel nitrate hexahydrate are weighed and added into 200ml of distilled water to prepare impregnation liquid, then the barium-calcium modified molecular sieve carrier is impregnated, the impregnation is carried out for 20h at normal temperature, the impregnation is carried out, the drying is carried out for 10h at the temperature of 110 ℃, the roasting is carried out for 3h at the temperature of 530 ℃, and 430.37g of desulfurization adsorbent 1 is obtained.
The desulfurization adsorbent 1 mainly comprises the following components: 6.88 wt% of copper oxide, 6.02 wt% of nickel oxide, 1.72 wt% of barium oxide, 1.72 wt% of calcium oxide and 83.66 wt% of micro-mesoporous molecular sieve carrier M-1.
The embodiment also provides a method for deeply desulfurizing the tetrakakyl hydrocarbon, which comprises the following steps:
adopting a 30ml fixed bed reactor, wherein the fixed bed reactor is filled with a desulfurization adsorbent 1;
introducing isobutane raw material into a reactor from the bottom of the fixed bed reactor, introducing the isobutane raw material into the fixed bed reactor for desulfurization treatment, wherein the temperature of the reactor is 25 ℃, the reaction pressure is 1.0MPa, and the liquid loading space velocity of the isobutane raw material is 2.0h-1And analyzing the sulfur content in the isobutane raw material at the outlet of the fixed bed reactor, and when the sulfur content in the isobutane raw material at the outlet of the fixed bed reactor reaches 1mg/kg, determining that the desulfurization adsorbent penetrates through the isobutane raw material, and stopping the experiment. The time from the initial reaction time to the time when the sulfur mass fraction of the outlet sample is higher than 1mg/kg is the breakthrough time of the desulfurization adsorbent. The mass fraction of sulfur element adsorbed on the desulfurization adsorbent during the breakthrough time is the breakthrough of the adsorbentAnd (4) sulfur capacity. The breakthrough time was 44 hours, and the reaction performance of the desulfurization adsorbent 1 is shown in table 3.
Example 2:
the embodiment provides a preparation method of a desulfurization adsorbent, which comprises the following steps:
weighing 220g of alumina-containing 25% alumina sol by using a beaker, and adding 16.0g of nitric acid with the concentration of 68% into the alumina sol to obtain an alumina sol nitric acid solution; and weighing 20.0g of polyvinyl alcohol pore-expanding agent, adding the polyvinyl alcohol pore-expanding agent into the prepared aluminum sol nitric acid solution, and uniformly stirring to obtain the aluminum sol nitric acid solution containing the pore-expanding agent.
300g of NaY molecular sieve raw powder and 15g of carboxymethyl cellulose are weighed and added into a kneader to be uniformly mixed, and then an aluminum sol nitric acid solution containing a pore-expanding agent is added to be continuously kneaded uniformly.
Kneading and extruding the mixture into a cylindrical shape, drying the cylindrical shape at 120 ℃ for 8 hours, and roasting the cylindrical shape at 600 ℃ for 4 hours to obtain the molecular sieve carrier M-2 with the micro-mesopores, wherein the specific surface area and the pore size distribution of the molecular sieve carrier are shown in Table 2.
Weighing 7.00g of barium nitrate and 31.48g of calcium nitrate tetrahydrate, adding the barium nitrate and the calcium nitrate tetrahydrate into 100ml of distilled water to prepare an auxiliary agent impregnation liquid, then impregnating 355.00g of micro-mesoporous molecular sieve carrier M-2, impregnating at normal temperature for 15h, drying at 110 ℃ for 10h after impregnation, and roasting at 550 ℃ for 4h to obtain 366.57g of barium calcium modified molecular sieve carrier.
Then 84.99g of copper nitrate trihydrate and 130.71g of nickel nitrate hexahydrate are weighed and added into 200ml of distilled water to prepare impregnation liquid, then the barium-calcium modified molecular sieve carrier is impregnated, the impregnation liquid is impregnated for 20 hours at normal temperature, the impregnation liquid is dried for 5 hours at the temperature of 130 ℃, and the impregnation liquid is roasted for 5 hours at the temperature of 500 ℃, so that 428.13g of desulfurization adsorbent 2 is obtained.
The desulfurization adsorbent 2 mainly comprises the following components: 6.54 wt% of copper oxide, 7.84 wt% of nickel oxide, 0.96 wt% of barium oxide, 1.74 wt% of calcium oxide and 82.92 wt% of micro-mesoporous molecular sieve carrier M-2.
The embodiment also provides a method for deeply desulfurizing the tetrakakyl hydrocarbon, which comprises the following steps:
a 30ml fixed bed reactor is adopted, and a desulfurization adsorbent 2 is filled in the fixed bed reactor;
introducing isobutane raw material into a reactor from the bottom of the fixed bed reactor, introducing the isobutane raw material into the fixed bed reactor for desulfurization treatment, wherein the temperature of the reactor is 25 ℃, the reaction pressure is 1.0MPa, and the liquid loading space velocity of the isobutane raw material is 2.0h-1And analyzing the sulfur content in the isobutane raw material at the outlet of the fixed bed reactor, and when the sulfur content in the isobutane raw material at the outlet of the fixed bed reactor reaches 1mg/kg, determining that the desulfurization adsorbent penetrates through the isobutane raw material, and stopping the experiment. The time from the initial reaction time to the time when the sulfur mass fraction of the outlet sample is higher than 1mg/kg is the breakthrough time of the desulfurization adsorbent. The mass fraction of elemental sulfur adsorbed on the desulfurization adsorbent during the breakthrough time is the breakthrough sulfur capacity of the adsorbent. The breakthrough time was 44 hours, and the reaction performance of the desulfurization adsorbent 2 is shown in table 3.
Example 3:
the embodiment provides a preparation method of a desulfurization adsorbent, which comprises the following steps:
200g of alumina 20% containing alumina was weighed in a beaker, and 11.0g of acetic acid was added to the alumina sol to obtain an alumina sol acetic acid solution; weighing 14.0g of polyvinyl alcohol pore-expanding agent, adding the polyvinyl alcohol pore-expanding agent into the prepared alumina sol acetic acid solution, and uniformly stirring to obtain the alumina sol acetic acid solution containing the pore-expanding agent.
300g of molecular sieve raw powder and 13g of carboxymethyl cellulose are weighed and added into a kneader to be uniformly mixed, and then an aluminum sol nitric acid solution containing a pore-expanding agent is added to be continuously kneaded uniformly.
Kneading and extruding the mixture into a cylindrical shape, drying the cylindrical shape at 120 ℃ for 10 hours, and roasting the cylindrical shape at 500 ℃ for 4 hours to obtain the molecular sieve carrier M-3 with the micro-mesopores, wherein the specific surface area and the pore size distribution of the molecular sieve carrier are shown in Table 2.
Weighing 9.71g of barium nitrate and 64.07g of calcium nitrate tetrahydrate, adding the barium nitrate and the calcium nitrate tetrahydrate into 150ml of distilled water to prepare an auxiliary agent impregnation liquid, then impregnating 340.00g of a micro-mesoporous molecular sieve carrier M-3, impregnating at normal temperature for 18h, drying at 110 ℃ for 6h after impregnation, and roasting at 400 ℃ for 6h to obtain 360.89g of the barium calcium modified molecular sieve carrier.
Then 109.57g of copper nitrate trihydrate and 88.69g of nickel nitrate hexahydrate are weighed and added into 200ml of distilled water to prepare impregnation liquid, then the barium-calcium modified molecular sieve carrier is impregnated, the impregnation liquid is impregnated for 15h at normal temperature, then the drying is carried out for 5h at the temperature of 130 ℃, and the roasting is carried out for 9h at the temperature of 380 ℃, so as to obtain 419.75g of desulfurization adsorbent 3.
The desulfurization adsorbent 3 mainly comprises the following components: 8.59 wt% of copper oxide, 5.43 wt% of nickel oxide, 1.36 wt% of barium oxide, 3.62 wt% of calcium oxide and 81 wt% of micro-mesoporous molecular sieve carrier M-3.
The embodiment also provides a method for deeply desulfurizing the tetrakakyl hydrocarbon, which comprises the following steps:
a 30ml fixed bed reactor is adopted, and a desulfurization adsorbent 3 is filled in the fixed bed reactor;
introducing isobutane raw material into a reactor from the bottom of the fixed bed reactor, introducing the isobutane raw material into the fixed bed reactor for desulfurization treatment, wherein the temperature of the reactor is 25 ℃, the reaction pressure is 1.0MPa, and the liquid loading space velocity of the isobutane raw material is 2.0h-1And analyzing the sulfur content in the isobutane raw material at the outlet of the fixed bed reactor, and when the sulfur content in the isobutane raw material at the outlet of the fixed bed reactor reaches 1mg/kg, determining that the desulfurization adsorbent penetrates through the isobutane raw material, and stopping the experiment. The time from the initial reaction time to the time when the sulfur mass fraction of the outlet sample is higher than 1mg/kg is the breakthrough time of the desulfurization adsorbent. The mass fraction of elemental sulfur adsorbed on the desulfurization adsorbent during the breakthrough time is the breakthrough sulfur capacity of the adsorbent. The breakthrough time was 42 hours, and the reaction performance of the desulfurization adsorbent 3 is shown in table 3.
Example 4:
the embodiment provides a preparation method of a desulfurization adsorbent, which comprises the following steps:
weighing 200g of alumina sol containing 20% of alumina by using a beaker, and adding 16.0g of nitric acid with the concentration of 68% into the alumina sol to obtain an alumina sol nitric acid solution; and weighing 20.0g of polyvinyl alcohol pore-expanding agent, adding the polyvinyl alcohol pore-expanding agent into the prepared aluminum sol nitric acid solution, and uniformly stirring to obtain the aluminum sol nitric acid solution containing the pore-expanding agent.
300g of molecular sieve raw powder and 15g of carboxymethyl cellulose are weighed and added into a kneader to be uniformly mixed, and then an aluminum sol nitric acid solution containing a pore-expanding agent is added to be continuously kneaded uniformly.
Kneading and extruding the mixture into a cylindrical shape, drying the cylindrical shape at 120 ℃ for 8 hours, and roasting the cylindrical shape at 550 ℃ for 4 hours to obtain the molecular sieve carrier M-4 with the micro-mesopores, wherein the specific surface area and the pore size distribution of the molecular sieve carrier are shown in Table 2.
16.19g of barium nitrate and 24.03g of calcium nitrate tetrahydrate are weighed and added into 100ml of distilled water to prepare an auxiliary agent impregnation liquid, then 340g of micro-mesoporous molecular sieve carrier M-4 is impregnated, the micro-mesoporous molecular sieve carrier M-4 is impregnated at normal temperature for 15h, the impregnated micro-mesoporous molecular sieve carrier is dried at 110 ℃ for 10h, and the impregnated micro-mesoporous molecular sieve carrier is roasted at 3500 ℃ for 9h, so that 355.19g of barium calcium modified molecular sieve carrier is obtained.
Then 138.40g of copper nitrate trihydrate and 73.91g of nickel nitrate hexahydrate are weighed and added into 200ml of distilled water to prepare impregnation liquid, then the barium-calcium modified molecular sieve carrier is impregnated, the impregnation is carried out for 16h at normal temperature, the impregnation is carried out, the drying is carried out for 5h at the temperature of 110 ℃, the roasting is carried out for 3h at the temperature of 380 ℃, and 419.75g of desulfurization adsorbent 4 is obtained.
The desulfurization adsorbent 4 mainly comprises the following components: 10.86 wt% of copper oxide, 4.52 wt% of nickel oxide, 2.26 wt% of barium oxide, 1.36 wt% of calcium oxide and 81 wt% of micro-mesoporous molecular sieve carrier M-4.
The embodiment also provides a method for deeply desulfurizing the tetrakakyl hydrocarbon, which comprises the following steps:
a 30ml fixed bed reactor is adopted, and a desulfurization adsorbent 4 is filled in the fixed bed reactor;
introducing isobutane raw material into a reactor from the bottom of the fixed bed reactor, introducing the isobutane raw material into the fixed bed reactor for desulfurization treatment, wherein the temperature of the reactor is 25 ℃, the reaction pressure is 1.0MPa, and the liquid loading space velocity of the isobutane raw material is 2.0h-1And analyzing the sulfur content in the isobutane raw material at the outlet of the fixed bed reactor, and when the sulfur content in the isobutane raw material at the outlet of the fixed bed reactor reaches 1mg/kg, determining that the desulfurization adsorbent penetrates through the isobutane raw material, and stopping the experiment. The time from the initial reaction time to the time when the sulfur mass fraction of the outlet sample is higher than 1mg/kg is the breakthrough time of the desulfurization adsorbent. The mass fraction of elemental sulfur adsorbed on the desulfurization adsorbent during the breakthrough time is the breakthrough sulfur capacity of the adsorbent. The breakthrough time was 49 hours, and the reaction performance of the desulfurization adsorbent 4 is shown in table 3.
Example 5:
the embodiment provides a preparation method of a desulfurization adsorbent, which comprises the following steps:
weighing 200g of alumina sol containing 20% of alumina by using a beaker, and adding 8.0g of nitric acid with the concentration of 68% into the alumina sol to obtain an alumina sol nitric acid solution; 25.0g of polyvinyl alcohol pore-expanding agent is weighed and added into the prepared aluminum sol nitric acid solution, and the mixture is uniformly stirred to obtain the aluminum sol nitric acid solution containing the pore-expanding agent.
300g of molecular sieve raw powder and 15g of carboxymethyl cellulose are weighed and added into a kneader to be uniformly mixed, and then an aluminum sol nitric acid solution containing a pore-expanding agent is added to be continuously kneaded uniformly.
Kneading and extruding the mixture into a cylindrical shape, drying the cylindrical shape at 120 ℃ for 8 hours, and roasting the cylindrical shape at 550 ℃ for 4 hours to obtain the molecular sieve carrier M-5 with the micro-mesopores, wherein the specific surface area and the pore size distribution of the molecular sieve carrier are shown in Table 2.
Weighing 6.73g of barium nitrate and 16.65g of calcium nitrate tetrahydrate, adding the barium nitrate and the calcium nitrate tetrahydrate into 120ml of distilled water to prepare an auxiliary agent impregnation liquid, then impregnating 340.00g of the micro-mesoporous molecular sieve carrier M-5, impregnating at normal temperature for 15h, drying at 110 ℃ for 8h after impregnation, and roasting at 380 ℃ for 8h to obtain 347.89g of the barium calcium modified molecular sieve carrier.
And then adding 191.8g of copper nitrate trihydrate and 92.19g of nickel nitrate hexahydrate into 200ml of distilled water to prepare impregnation liquid, then impregnating the barium-calcium modified molecular sieve carrier, impregnating at normal temperature for 18h, drying at 130 ℃ for 5h after impregnation, and roasting at 480 ℃ for 6h to obtain 434.74g of desulfurization adsorbent 5.
The desulfurization adsorbent 5 mainly comprises the following components: 14.53 wt% of copper oxide, 5.45 wt% of nickel oxide, 0.91 wt% of barium oxide, 0.91 wt% of calcium oxide and 78.2 wt% of micro-mesoporous molecular sieve carrier M-5.
The embodiment also provides a method for deeply desulfurizing the tetrakakyl hydrocarbon, which comprises the following steps:
adopting a 30ml fixed bed reactor, wherein a desulfurization adsorbent 5 is filled in the fixed bed reactor;
introducing isobutane raw material into the reactor from the bottom of the fixed bed reactor to be fixedCarrying out desulfurization treatment in a bed reactor, wherein the temperature of the reactor is 25 ℃, the reaction pressure is 1.0MPa, and the space velocity of the isobutane bulk liquid is 2.0h-1And analyzing the sulfur content in the isobutane raw material at the outlet of the fixed bed reactor, and when the sulfur content in the isobutane raw material at the outlet of the fixed bed reactor reaches 1mg/kg, determining that the desulfurization adsorbent penetrates through the isobutane raw material, and stopping the experiment. The time from the initial reaction time to the time when the sulfur mass fraction of the outlet sample is higher than 1mg/kg is the breakthrough time of the desulfurization adsorbent. The mass fraction of elemental sulfur adsorbed on the desulfurization adsorbent during the breakthrough time is the breakthrough sulfur capacity of the adsorbent. The breakthrough time was 43 hours, and the reaction performance of the desulfurization adsorbent 5 is shown in table 3.
Example 6:
the embodiment provides a preparation method of a desulfurization adsorbent, which comprises the following steps:
weighing 200g of alumina sol containing 20% of alumina by using a beaker, and adding 12.0g of nitric acid with the concentration of 68% into the alumina sol to obtain an alumina sol nitric acid solution; and weighing 20.0g of polyvinyl alcohol pore-expanding agent, adding the polyvinyl alcohol pore-expanding agent into the prepared aluminum sol nitric acid solution, and uniformly stirring to obtain the aluminum sol nitric acid solution containing the pore-expanding agent.
300g of molecular sieve raw powder and 15g of carboxymethyl cellulose are weighed and added into a kneader to be uniformly mixed, and then an aluminum sol nitric acid solution containing a pore-expanding agent is added to be continuously kneaded uniformly.
Kneading and extruding the mixture into a cylindrical shape, drying the cylindrical shape at 120 ℃ for 8 hours, and roasting the cylindrical shape at 500 ℃ for 4 hours to obtain the molecular sieve carrier M-6 with the micro-mesopores, wherein the specific surface area and the pore size distribution of the molecular sieve carrier are shown in Table 2.
Weighing 6.48g of barium nitrate and 64.07g of calcium nitrate tetrahydrate, adding the barium nitrate and the calcium nitrate tetrahydrate into 150ml of distilled water to prepare an auxiliary agent impregnation liquid, then impregnating 340.00g of a micro-mesoporous molecular sieve carrier M-6, impregnating at normal temperature for 16h, drying at 110 ℃ for 10h after impregnation, and roasting at 480 ℃ for 9h to obtain 358.99g of the barium calcium modified molecular sieve carrier.
Then 46.13g of copper nitrate trihydrate and 177.37g of nickel nitrate hexahydrate are weighed and added into 200ml of distilled water to prepare impregnation liquid, then the barium-calcium modified molecular sieve carrier is impregnated, the impregnation liquid is impregnated for 20h at normal temperature, the impregnated molecular sieve carrier is dried for 8h at the temperature of 130 ℃, and the impregnated molecular sieve carrier is roasted for 7h at the temperature of 480 ℃, so that 419.75g of desulfurization adsorbent 6 is obtained.
The desulfurization adsorbent 6 mainly comprises the following components: 3.62 wt% of copper oxide, 10.86 wt% of nickel oxide, 0.90 wt% of barium oxide, 3.62 wt% of calcium oxide and 81 wt% of micro-mesoporous molecular sieve carrier M-6.
The embodiment also provides a method for deeply desulfurizing the tetrakakyl hydrocarbon, which comprises the following steps:
a 30ml fixed bed reactor is adopted, and a desulfurization adsorbent 6 is filled in the fixed bed reactor;
introducing isobutane raw material into a reactor from the bottom of the fixed bed reactor, introducing the isobutane raw material into the fixed bed reactor for desulfurization treatment, wherein the temperature of the reactor is 25 ℃, the reaction pressure is 1.0MPa, and the liquid loading space velocity of the isobutane raw material is 2.0h-1And analyzing the sulfur content in the isobutane raw material at the outlet of the fixed bed reactor, and when the sulfur content in the isobutane raw material at the outlet of the fixed bed reactor reaches 1mg/kg, determining that the desulfurization adsorbent penetrates through the isobutane raw material, and stopping the experiment. The time from the initial reaction time to the time when the sulfur mass fraction of the outlet sample is higher than 1mg/kg is the breakthrough time of the desulfurization adsorbent. The mass fraction of elemental sulfur adsorbed on the desulfurization adsorbent during the breakthrough time is the breakthrough sulfur capacity of the adsorbent. The breakthrough time was 46 hours, and the reaction performance of the desulfurization adsorbent 6 is shown in table 3.
Comparative example 1:
the present comparative example provides a method for preparing a desulfurization adsorbent, comprising the steps of:
240g of alumina-containing 25% alumina sol was weighed in a beaker, and 14.0g of oxalic acid was added to the alumina sol to be uniformly mixed, and then added to the alumina sol to obtain an alumina sol oxalic acid solution.
300g of NaY molecular sieve raw powder and 15g of carboxymethyl cellulose are weighed and added into a kneader to be uniformly mixed, and then an alumina sol oxalic acid solution is added to be continuously kneaded uniformly.
Kneading and extruding to form the cylindrical shape. Then drying for 6 hours at 150 ℃, and roasting for 5 hours at 600 ℃ to obtain the molecular sieve carrier N-1, wherein the specific surface area and the pore size distribution are shown in Table 2.
Weighing 12.63g of barium nitrate and 31.24g of calcium nitrate tetrahydrate, adding the barium nitrate and the calcium nitrate tetrahydrate into 100ml of distilled water to prepare an auxiliary agent impregnation liquid, then impregnating 360g of microporous molecular sieve carrier N-1, impregnating at normal temperature for 20h, drying at 110 ℃ for 8h after impregnation, and roasting at 530 ℃ for 3h to obtain 374.81g of barium calcium modified molecular sieve carrier.
And then 89.98g of copper nitrate trihydrate and 100.91g of nickel nitrate hexahydrate are weighed and added into 200ml of distilled water to prepare impregnation liquid, then the barium-calcium modified molecular sieve carrier is impregnated, the impregnation liquid is impregnated for 20 hours at normal temperature, the impregnation liquid is dried for 10 hours at the temperature of 110 ℃, and the impregnation liquid is roasted for 3 hours at the temperature of 530 ℃, so that the desulfurization adsorbent D-1 is obtained.
The desulfurization adsorbent D-1 mainly comprises the following components: 6.88 weight percent of copper oxide, 6.02 weight percent of nickel oxide, 1.72 weight percent of barium oxide, 1.72 weight percent of calcium oxide and 83.66 weight percent of molecular sieve carrier N-1.
The desulfurization test of the desulfurization adsorbent D-1 was conducted in the same manner as in example 1.
Comparative example 2:
the present comparative example provides a method for preparing a desulfurization adsorbent, comprising the steps of:
the preparation process of the mesoporous molecular sieve carrier M-1 is the same as that of example 1.
Weighing 12.63g of barium nitrate and 31.24g of calcium nitrate tetrahydrate, adding the barium nitrate and the calcium nitrate tetrahydrate into 100ml of distilled water to prepare an auxiliary agent impregnation liquid, then impregnating 360g of a micro-mesoporous molecular sieve carrier M-1, impregnating at normal temperature for 20h, drying at 110 ℃ for 8h after impregnation, and roasting at 530 ℃ for 3h to obtain 374.81g of the barium calcium modified molecular sieve carrier.
And then 89.98g of copper nitrate trihydrate is weighed and added into 120ml of distilled water to prepare impregnation liquid, the barium-calcium modified molecular sieve carrier is impregnated at normal temperature for 20 hours, and after impregnation, the barium-calcium modified molecular sieve carrier is dried at 110 ℃ for 10 hours and roasted at 530 ℃ for 3 hours to obtain 404.47g of desulfurization adsorbent D-2.
The desulfurization adsorbent D-2 mainly comprises the following components: 7.32 wt% of copper oxide, 1.83 wt% of barium oxide, 1.83 wt% of calcium oxide and 89.02 wt% of micro-mesoporous molecular sieve carrier M-1.
The desulfurization test of the desulfurization adsorbent D-2 was conducted in the same manner as in example 1.
Comparative example 3:
the present comparative example provides a method for preparing a desulfurization adsorbent, comprising the steps of:
the preparation process of the mesoporous molecular sieve carrier M-1 is the same as that of example 1.
Weighing 12.63g of barium nitrate and 31.24g of calcium nitrate tetrahydrate, adding the barium nitrate and the calcium nitrate tetrahydrate into 100ml of distilled water to prepare an auxiliary agent impregnation liquid, then impregnating 360g of a micro-mesoporous molecular sieve carrier M-1, impregnating at normal temperature for 20h, drying at 110 ℃ for 8h after impregnation, and roasting at 530 ℃ for 3h to obtain 374.81g of the barium calcium modified molecular sieve carrier.
Then weighing 100.91g of nickel nitrate hexahydrate and adding the nickel nitrate hexahydrate into 200ml of distilled water to prepare impregnation liquid, then impregnating the barium-calcium modified molecular sieve carrier, impregnating for 20 hours at normal temperature, drying for 10 hours at 110 ℃ after impregnation, and roasting for 3 hours at 530 ℃ to obtain 400.74g of desulfurization adsorbent D-3.
The desulfurization adsorbent D-3 mainly comprises the following components: 6.47 wt% of nickel oxide, 1.85 wt% of calcium oxide, 1.85 wt% of barium oxide and 89.83 wt% of micro-mesoporous molecular sieve carrier M-1.
The desulfurization test of the desulfurization adsorbent D-3 was conducted in the same manner as in example 1.
The following table 2 is a table of the specific surface area and pore size distribution of the mesoporous molecular sieve carrier, and the following table 3 is a table of the performance evaluation results of the desulfurization adsorbent.
Table 2:
Figure BDA0002653024560000121
table 3:
Figure BDA0002653024560000122
as can be seen from the data represented in Table 2, the total pore volume of the adsorbent added with the pore-forming agent is significantly increased, and the average pore diameter of the mesopores is also significantly higher than that of the adsorbent without the pore-forming agent, which indicates that the mesopores can be significantly introduced into the adsorbent system by the addition of the pore-forming agent.
As can be seen from the experimental data in table 3: the desulfurization performance of the desulfurization adsorbent added with the four metals of copper, nickel, barium and calcium is obviously higher than that of the desulfurization adsorbent added with three or two metals, the penetration time of the desulfurization adsorbent added with the four metals is longer, the sulfur capacity is higher, and the penetration sulfur capacity of the desulfurization adsorbent can reach more than 4.7%.

Claims (10)

1. A desulfurization adsorbent, comprising, in 100 wt% by weight:
Figure FDA0002653024550000011
2. the desulfurization sorbent of claim 1, wherein the desulfurization sorbent comprises, in weight percent 100 wt%:
Figure FDA0002653024550000012
3. the desulfurization adsorbent according to claim 1 or 2, wherein the micro-mesoporous molecular sieve support has a pore size distribution of 1 to 15nm, a total pore volume of 0.3 to 0.5ml/g, and a specific surface area of 500 to 550m2/g；
Wherein the pore diameter distribution of the micropores is 1-2 nm, and the pore volume of the micropores accounts for 40% -80% of the total pore volume; the mesoporous aperture distribution is 8-15 nm, and the mesoporous volume accounts for 20-60% of the total pore volume.
4. A method for preparing the desulfurization adsorbent according to any one of claims 1 to 3, which comprises the steps of:
mixing soluble barium salt and soluble calcium salt, adding water to prepare a first impregnation solution, impregnating a micro mesoporous molecular sieve carrier in the first impregnation solution, drying after impregnation, and roasting to obtain a barium-calcium modified carrier;
and mixing soluble copper salt and soluble nickel salt, adding water to prepare a second impregnation solution, impregnating the barium-calcium modified carrier in the second impregnation solution, drying after impregnation, and roasting to obtain the desulfurization adsorbent.
5. The production method according to claim 4, wherein the soluble barium salt comprises barium nitrate and/or barium chloride; the soluble calcium salt comprises calcium nitrate and/or calcium chloride; the soluble copper salt comprises copper nitrate and/or copper chloride; the soluble nickel salt comprises nickel nitrate and/or nickel chloride;
preferably, the soluble barium salt, the soluble calcium salt, the soluble copper salt and the soluble nickel salt are all nitrates thereof.
6. The preparation method according to claim 4, wherein the first impregnation liquid is immersed at normal temperature for 12-20 h; drying at 90-140 ℃ for 4-10 h after dipping; the roasting temperature after drying is 350-550 ℃, and the roasting time is 4-9 h;
preferably, the second impregnation liquid is impregnated at normal temperature for 12-20 hours; drying at 90-140 ℃ for 4-10 h after dipping; the roasting temperature after drying is 350-550 ℃, and the roasting time is 4-9 h.
7. The preparation method according to claim 4, wherein the preparation method of the micro mesoporous molecular sieve support comprises the following steps:
adding organic acid and/or inorganic acid into the aluminum sol to obtain an aluminum sol acid solution, and then dissolving the pore-expanding agent into the aluminum sol acid solution to obtain an aluminum sol acid solution containing the pore-expanding agent;
adding molecular sieve powder and carboxymethyl cellulose into a kneader, uniformly mixing, adding an aluminum sol acid solution containing a pore-expanding agent, and continuously kneading uniformly;
the molecular sieve carrier with the micro-mesoporous structure is obtained through extrusion, molding, drying and roasting.
8. The production method according to claim 7, wherein the mass ratio of the pore-expanding agent to the aluminum sol is 1: (4-20); in the aluminum sol, the content of aluminum oxide is 20-25 wt%;
preferably, the pore-expanding agent comprises polyvinyl alcohol;
preferably, the organic acid comprises oxalic acid and/or citric acid; the inorganic acid comprises nitric acid and/or hydrochloric acid;
preferably, the molecular sieve powder comprises one or more of raw powder of NaY molecular sieve, raw powder of NaX molecular sieve, raw powder of ZSM-5 molecular sieve and raw powder of MCM-41 molecular sieve;
preferably, the amount of the organic acid and/or the inorganic acid is 2 to 35 weight percent of the pore-expanding agent;
preferably, the mass ratio of the pore-expanding agent to the molecular sieve powder is 1: (10-50);
preferably, the mass ratio of the molecular sieve powder to the carboxymethyl cellulose is (10-30): 1;
preferably, the drying temperature after the extrusion molding is 90-140 ℃, and the drying time is 4-10 h; the roasting temperature after drying is 350-550 ℃, and the roasting time is 4-9 h.
9. A method for deeply desulfurizing a tetracarbon hydrocarbon, comprising the steps of:
adopting a fixed bed reactor, wherein the desulfurization adsorbent is filled in the fixed bed reactor according to any one of claims 1 to 3;
and introducing the tetrakam into a fixed bed reactor for desulfurization treatment to obtain desulfurized tetrakam.
10. The method of claim 9, wherein the reaction temperature is 0-80 ℃, the reaction pressure is 0.4-2.5 MPa, and the space velocity of the liquid volume of the tetracarbon is 0.2-5.0 h during the desulfurization process-1；
Preferably, in the desulfurization process, the reaction temperature is 10-70 ℃, the reaction pressure is 0.6-2.0 MPa, and the space velocity of the liquid volume of the carbon-tetralkyl hydrocarbon is 0.5-4.0 h-1。
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