CN111974340B - Desulfurizing adsorbent, preparation method thereof and deep desulfurization method of carbon tetraalkylalkane - Google Patents
Desulfurizing adsorbent, preparation method thereof and deep desulfurization method of carbon tetraalkylalkane Download PDFInfo
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Abstract
The invention provides a desulfurization adsorbent, a preparation method thereof and a deep desulfurization method of carbon tetraalkylalkane. The desulfurization adsorbent comprises, in weight percent, 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 higher adsorption desulfurization activity, strong selectivity and high sulfur capacity; the method is used for deep desulfurization of the carbon tetraalkoxide, has mild operation conditions, flexible adaptability to the raw materials of the carbon tetraalkoxide and high desulfurization efficiency.
Description
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 deep desulfurization method of carbon tetraalkylalkanes.
Background
Isobutene is used as an important basic organic chemical raw material, and has wide application and expanded demand and purpose. The isobutane dehydrogenation technology is one of the effective methods for increasing the yield of isobutene. As one of the raw materials for dehydrogenation, the composition of the carbon tetraalkylalkane is relatively complex. Because of different sources, different production processes and different transportation processes, the carbon tetraalkylalkanes often contain unequal amounts of sulfur-containing compounds, oxygen-containing compounds and nitrogen-containing compounds. The polarity of the sulfur-containing compound in the impurities is stronger, and the byproduct isobutane contains impurities such as sulfur dioxide, so that the downstream carbon tetra-alkane dehydrogenation catalyst can be poisoned and deactivated. Therefore, in order to fully and reasonably utilize the tetraalkane, deep desulfurization of the tetraalkane is necessary, and the deep desulfurization of the tetraalkane is also becoming a key for further processing and utilization of the tetraalkane.
At present, the method for removing sulfides in the tetra-alkane mainly comprises three methods of hydrogenation, alkali washing and adsorption. The hydrogenation method requires a special catalyst, and because part of sulfides are difficult to hydrogenate, deep hydrogenation is required for hydrogenation and removal, so that the energy consumption is high and the economical efficiency is poor. The alkaline washing method mainly uses alkali as an absorbent, and has high sulfide removal efficiency and easy operation and control, but has the problem of post-treatment of waste alkali liquor, and meanwhile, the effect of deep sulfide removal is difficult to achieve by alkaline washing. The adsorption method has simple process, low energy consumption, no corrosion and no pollution, and especially the purification depth of adsorption is far higher than that of hydrogenation and alkali washing processes when the sulfide content is very low, so that the adsorption is more suitable for deep removal of the sulfide of the raw material.
However, the existing desulfurization adsorbent has low desulfurization efficiency, poor desulfurization precision and low sulfur capacity, and cannot meet the deep desulfurization of the tetraalkane.
Disclosure of Invention
Based on the problems existing in the prior art, the first object of the invention is to provide a desulfurization adsorbent, which is obtained by taking a step pore molecular sieve containing micropores and mesopores as a carrier, doping barium and calcium and loading copper and nickel; a second object of the present invention is to provide a method for producing the desulfurization adsorbent; a third object of the present invention is to provide a method for deep desulfurization of a tetraalkane using the desulfurization adsorbent.
The aim of the invention is achieved by the following technical scheme:
in one aspect, the present invention provides a desulfurization adsorbent comprising, in weight percent 100 wt%:
in the desulfurization adsorbent, the acidity of the surface of the carrier can be regulated by doping barium and calcium elements, so that the dispersity and 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 includes, in weight percentage, 100 wt%:
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 m 2 /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 pore diameter distribution is 8-15 nm, and the mesoporous volume accounts for 20-60% of the total pore volume.
The micro mesoporous molecular sieve carrier does not need to add reagents such as dispersing agents, chelating agents and the like, the preparation cost is greatly reduced, the added pore-expanding agent is easy to obtain, and the preparation process is easy to popularize. The micro-mesoporous carrier has two advantages, namely, the specific surface area is high, and the load of the metal active components is uniform; secondly, the mass transfer resistance is smaller, the diffusion of sulfide during adsorption is faster, and the adsorption effect is better.
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 impregnating solution, impregnating a micro-mesoporous molecular sieve carrier in the first impregnating solution, and drying and roasting after impregnation to obtain a barium-calcium modified carrier;
mixing soluble copper salt and soluble nickel salt, adding water to prepare a second impregnating solution, impregnating a barium-calcium modified carrier in the second impregnating solution, drying and roasting after impregnation to obtain the desulfurization adsorbent.
In the preparation method, the dosage of the soluble barium salt, the soluble calcium salt, the soluble copper salt, the soluble nickel salt, the micro-mesoporous molecular sieve carrier and the water is properly adjusted according to actual operation so as to meet the condition that the contents of the micro-mesoporous molecular sieve carrier, the copper oxide, the nickel oxide, the barium oxide and the calcium oxide in the desulfurization adsorbent obtained by final roasting meet 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 and the like; 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 nitrate salts thereof.
In the above preparation method, preferably, the temperature of the first impregnation liquid is normal temperature, and the impregnation time is 12-20 hours; the temperature of drying after dipping is 90-140 ℃ and the time of drying is 4-10 h; the roasting temperature after drying is 350-550 ℃ and the roasting time is 4-9 h.
In the above preparation method, preferably, the temperature of the second impregnation liquid is normal temperature, and the impregnation time is 12-20 hours; the temperature of drying after dipping is 90-140 ℃ and the time of drying is 4-10 h; 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 micro mesoporous molecular sieve carrier includes:
adding organic acid and/or inorganic acid into the aluminum sol to obtain an aluminum sol acidic solution, and then dissolving a pore-expanding agent into the aluminum sol acidic 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, and then adding aluminum sol acid liquor containing a pore-expanding agent for continuous uniform kneading;
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 mass content of aluminum oxide is 20-25 wt%.
In the above preparation method, preferably, the pore-expanding agent may include polyvinyl alcohol and the like.
The invention adopts the polyvinyl alcohol as the pore-expanding agent, has good solubility and stability, can lead the molecular sieve carrier to generate micropore and mesoporous structures more easily, and can obtain the micro-mesoporous structure with adjustable pore size distribution, 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, etc.; the inorganic acid includes nitric acid and/or hydrochloric acid, etc.
In the above preparation method, preferably, the molecular sieve powder includes one or more of NaY molecular sieve raw powder, naX molecular sieve raw powder, ZSM-5 molecular sieve raw powder, MCM-41 molecular sieve raw powder, and the like.
In the above preparation method, preferably, the amount of the organic acid and/or the inorganic acid is 2wt% to 35wt% of the pore-expanding agent.
In the above preparation method, preferably, the mass ratio of the molecular sieve powder to the carboxymethyl cellulose is (10 to 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 above preparation method, preferably, the temperature of drying after extrusion molding is 90-140 ℃ and the drying time is 4-10 h; the baking temperature after drying is 350-550 ℃, and the baking time is 4-9 h.
In yet another aspect, the present invention also provides a method for deep desulfurization of a tetraalkane, comprising the steps of:
a fixed bed reactor is adopted, and the desulfurization adsorbent is filled in the fixed bed reactor;
introducing the carbon tetra-alkane into a fixed bed reactor for desulfurization treatment to obtain the desulfurized carbon tetra-alkane.
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 volume liquid space velocity of the carbon tetra-alkane 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 volume liquid space velocity of the carbon tetra-alkane is 0.5-4.0 h -1 。
The desulfurization adsorbent has higher adsorption desulfurization activity, strong selectivity and high sulfur capacity; the method is used for deep desulfurization of the carbon tetraalkoxide, and has the advantages of mild operation conditions, flexible adaptability to the raw materials of the carbon tetraalkoxide and high desulfurization efficiency.
Drawings
FIG. 1 is a graph showing pore size distribution of a micro-mesoporous molecular sieve carrier prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
The isobutane feed in the examples below was derived from isobutane feed separated in a sulfuric acid alkylation unit and the composition is shown in table 1:
table 1:
| component (A) | Content/w% |
| Propane | 0.58 |
| Isobutane | 89.16 |
| N-butane | 9.63 |
| C 5+ | 0.58 |
The analysis method adopts an ultraviolet fluorescence sulfur determination instrument to determine the sulfur content of the isobutane raw material obtained by separation of an alkylation device before and after desulfurization, and the sulfur dioxide content of the isobutane raw material before desulfurization is 280mg/kg.
Example 1:
the embodiment provides a method for preparing a desulfurization adsorbent, which comprises the following steps:
weighing 240g of alumina-containing 25% alumina sol by using a beaker, adding 5.0g of oxalic acid into the alumina sol, uniformly mixing the mixture, and adding the mixture 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 aluminum sol oxalic acid solution, and the mixture is stirred uniformly to obtain the aluminum 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 aluminum sol oxalic acid solution containing a pore-expanding agent is added to be continuously and uniformly kneaded.
Kneading, extruding to form cylindrical shape, drying at 110deg.C for 8 hr, and calcining at 550deg.C for 4 hr to obtain micro-mesoporous molecular sieve carrier M-1 with specific surface area and pore size distribution shown in Table 2. FIG. 1 is a graph showing the pore size distribution of the micro-mesoporous molecular sieve carrier M-1.
As can be seen from FIG. 1, the micro-mesoporous molecular sieve carrier M-1 prepared in this example has a more concentrated pore size distribution between the pore size range of 2nm and the pore size range of 6-14 nm, which indicates that the micro-mesoporous molecular sieve carrier M-1 prepared has a composite stepped pore structure.
12.63g of barium nitrate and 31.24g of calcium nitrate tetrahydrate are weighed and added into 100ml of distilled water to prepare auxiliary agent impregnating solution, then 360g of micro-mesoporous molecular sieve carrier M-1 is impregnated for 20 hours at normal temperature, the impregnated material is dried for 8 hours at 110 ℃ and baked for 3 hours at 530 ℃ to obtain 374.8g of barium-calcium modified molecular sieve carrier.
Then 89.98g of copper nitrate hexahydrate and 100.91g of nickel nitrate hexahydrate are weighed and added into 200ml of distilled water to prepare impregnating solution, then the barium-calcium modified molecular sieve carrier is impregnated for 20 hours at normal temperature, and after the impregnation, the molecular sieve carrier is dried for 10 hours at 110 ℃ and baked for 3 hours at 530 ℃ to obtain 430.37g of desulfurization adsorbent 1.
The desulfurization adsorbent 1 mainly comprises the following components: 6.88wt% of copper oxide, 6.02wt% of nickel oxide, 1.72wt% of barium oxide, 1.72wt% of calcium oxide and 83.66wt% of micro-mesoporous molecular sieve carrier M-1.
The embodiment also provides a deep desulfurization method for the carbon tetra-alkane, which comprises the following steps:
a 30ml fixed bed reactor is adopted, and the fixed bed reactor is filled with desulfurization adsorbent 1;
introducing isobutane raw material into a reactor from the bottom of a 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 space velocity of the volume liquid of the isobutane raw material is 2.0h -1 And analyzing the sulfur content in the isobutane raw material at the outlet of the fixed bed reactor, and stopping the experiment when the sulfur content in the isobutane raw material at the outlet of the fixed bed reactor reaches 1mg/kg, considering that the desulfurization adsorbent penetrates. The time from the initial reaction time to the outlet sample sulfur mass fraction of the desulfurization adsorbent higher than 1mg/kg is the penetration time of the desulfurization adsorbent. And in the penetrating time, the mass fraction of the sulfur element adsorbed on the desulfurization adsorbent is the penetrating sulfur capacity of the adsorbent. The breakthrough time was 44 hours, and the reactivity of desulfurization adsorbent 1 is shown in Table 3.
Example 2:
the embodiment provides a method for preparing a desulfurization adsorbent, which comprises the following steps:
220g of alumina-containing 25% alumina sol was weighed in a beaker, and 16.0g of 68% nitric acid was added to the alumina sol to obtain an alumina sol nitric acid solution; 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 aluminum sol nitric acid solution containing a pore-expanding agent is added to be continuously and uniformly kneaded.
Kneading, extruding to form cylindrical shape, drying at 120deg.C for 8 hr, and calcining at 600deg.C for 4 hr to obtain micro-mesoporous molecular sieve carrier M-2 with specific surface area and pore size distribution shown in Table 2.
7.00g of barium nitrate and 31.48g of calcium nitrate tetrahydrate are weighed and added into 100ml of distilled water to prepare auxiliary agent impregnating solution, then 355.00g of micro-mesoporous molecular sieve carrier M-2 is impregnated for 15 hours at normal temperature, after impregnation, the mixture is dried for 10 hours at 110 ℃, and baked for 4 hours at 550 ℃, thus obtaining 366.57g of barium-calcium modified molecular sieve carrier.
Then 84.99g of copper nitrate hexahydrate and 130.71g of nickel nitrate hexahydrate are weighed and added into 200ml of distilled water to prepare impregnating solution, then the barium-calcium modified molecular sieve carrier is impregnated for 20 hours at normal temperature, and after the impregnation, the molecular sieve carrier is dried for 5 hours at 130 ℃ and baked for 5 hours at 500 ℃ to obtain 428.13g of desulfurization adsorbent 2.
The desulfurization adsorbent 2 mainly comprises the following components: 6.54wt% of copper oxide, 7.84wt% of nickel oxide, 0.96wt% of barium oxide, 1.74wt% of calcium oxide and 82.92wt% of micro-mesoporous molecular sieve carrier M-2.
The embodiment also provides a deep desulfurization method for the carbon tetra-alkane, which comprises the following steps:
a 30ml fixed bed reactor is adopted, and the fixed bed reactor is filled with desulfurization adsorbent 2;
introducing isobutane raw material into a reactor from the bottom of a 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 space velocity of the volume liquid of the isobutane raw material is 2.0h -1 And analyzing the sulfur content in the isobutane raw material at the outlet of the fixed bed reactor, and stopping the experiment when the sulfur content in the isobutane raw material at the outlet of the fixed bed reactor reaches 1mg/kg, considering that the desulfurization adsorbent penetrates. The time from the initial reaction time to the outlet sample sulfur mass fraction of the desulfurization adsorbent higher than 1mg/kg is the penetration time of the desulfurization adsorbent. And in the penetrating time, the mass fraction of the sulfur element adsorbed on the desulfurization adsorbent is the penetrating sulfur capacity of the adsorbent. The breakthrough time was 44 hours and the reactivity of desulfurization adsorbent 2 is shown in table 3.
Example 3:
the embodiment provides a method for preparing a desulfurization adsorbent, which comprises the following steps:
200g of alumina-containing 20% alumina sol 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; 14.0g of polyvinyl alcohol pore-expanding agent is weighed and added into the prepared aluminum sol acetic acid solution, and the mixture is stirred uniformly to obtain the aluminum 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 mixed uniformly, and then aluminum sol nitric acid solution containing a pore-expanding agent is added to be kneaded uniformly continuously.
Kneading, extruding to form cylindrical shape, drying at 120deg.C for 10 hr, and calcining at 500deg.C for 4 hr to obtain micro-mesoporous molecular sieve carrier M-3 with specific surface area and pore size distribution shown in Table 2.
9.71g of barium nitrate and 64.07g of calcium nitrate tetrahydrate are weighed and added into 150ml of distilled water to prepare auxiliary agent impregnating solution, then 340.00g of micro-mesoporous molecular sieve carrier M-3 is impregnated for 18 hours at normal temperature, after the impregnation, the mixture is dried for 6 hours at 110 ℃, and baked for 6 hours at 400 ℃, thus obtaining 360.89g of barium-calcium modified molecular sieve carrier.
Then 109.57g of copper nitrate hexahydrate and 88.69g of nickel nitrate hexahydrate are weighed and added into 200ml of distilled water to prepare impregnating solution, then the barium-calcium modified molecular sieve carrier is impregnated, the molecular sieve carrier is impregnated for 15 hours at normal temperature, then dried for 5 hours at 130 ℃ and baked for 9 hours at 380 ℃ to obtain 419.75g of desulfurization adsorbent 3.
The desulfurization adsorbent 3 mainly comprises the following components: 8.59 weight percent of copper oxide, 5.43 weight percent of nickel oxide, 1.36 weight percent of barium oxide, 3.62 weight percent of calcium oxide and 81 weight percent of micro-mesoporous molecular sieve carrier M-3.
The embodiment also provides a deep desulfurization method for the carbon tetra-alkane, which comprises the following steps:
a 30ml fixed bed reactor is adopted, and the fixed bed reactor is filled with desulfurization adsorbent 3;
introducing isobutane raw material into a reactor from the bottom of a 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 space velocity of the volume liquid of the isobutane raw material is 2.0h -1 Analysis of sulfur in isobutane feedstock at fixed bed reactor outletContent, when the sulfur content in the isobutane feed at the outlet of the fixed bed reactor reached 1mg/kg, the desulfurization adsorbent was considered to penetrate, and the experiment was stopped. The time from the initial reaction time to the outlet sample sulfur mass fraction of the desulfurization adsorbent higher than 1mg/kg is the penetration time of the desulfurization adsorbent. And in the penetrating time, the mass fraction of the sulfur element adsorbed on the desulfurization adsorbent is the penetrating sulfur capacity of the adsorbent. The breakthrough time was 42 hours and the reactivity of desulfurization adsorbent 3 is shown in table 3.
Example 4:
the embodiment provides a method for preparing a desulfurization adsorbent, which comprises the following steps:
200g of alumina-containing 20% alumina sol was weighed in a beaker, and 16.0g of 68% nitric acid was added to the alumina sol to obtain an alumina sol nitric acid solution; 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 mixed uniformly, and then aluminum sol nitric acid solution containing a pore-expanding agent is added to be kneaded uniformly continuously.
Kneading, extruding to form cylindrical shape, drying at 120deg.C for 8 hr, and calcining at 550deg.C for 4 hr to obtain micro-mesoporous molecular sieve carrier M-4 with specific surface area and pore size distribution 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 auxiliary agent impregnating solution, then 340g of micro-mesoporous molecular sieve carrier M-4 is impregnated for 15 hours at normal temperature, the impregnated material is dried for 10 hours at 110 ℃, and baked for 9 hours at 3500 ℃ to obtain 355.19g of barium-calcium modified molecular sieve carrier.
Then 138.40g of copper nitrate hexahydrate and 73.91g of nickel nitrate hexahydrate are weighed and added into 200ml of distilled water to prepare impregnating solution, then the barium-calcium modified molecular sieve carrier is impregnated for 16 hours at normal temperature, the impregnated molecular sieve carrier is dried for 5 hours at 110 ℃ and baked for 3 hours at 380 ℃ to obtain 419.75g of desulfurization adsorbent 4.
The desulfurization adsorbent 4 mainly comprises the following components: 10.86wt% of copper oxide, 4.52wt% of nickel oxide, 2.26wt% of barium oxide, 1.36wt% of calcium oxide and 81wt% of micro-mesoporous molecular sieve carrier M-4.
The embodiment also provides a deep desulfurization method for the carbon tetra-alkane, which comprises the following steps:
a 30ml fixed bed reactor is adopted, and the fixed bed reactor is filled with desulfurization adsorbent 4;
introducing isobutane raw material into a reactor from the bottom of a 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 space velocity of the volume liquid of the isobutane raw material is 2.0h -1 And analyzing the sulfur content in the isobutane raw material at the outlet of the fixed bed reactor, and stopping the experiment when the sulfur content in the isobutane raw material at the outlet of the fixed bed reactor reaches 1mg/kg, considering that the desulfurization adsorbent penetrates. The time from the initial reaction time to the outlet sample sulfur mass fraction of the desulfurization adsorbent higher than 1mg/kg is the penetration time of the desulfurization adsorbent. And in the penetrating time, the mass fraction of the sulfur element adsorbed on the desulfurization adsorbent is the penetrating sulfur capacity of the adsorbent. The breakthrough time was 49 hours and the reactivity of desulfurization adsorbent 4 is shown in table 3.
Example 5:
the embodiment provides a method for preparing a desulfurization adsorbent, which comprises the following steps:
200g of alumina-containing 20% alumina sol was weighed in a beaker, and 8.0g of 68% nitric acid was added to 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 stirred uniformly 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 mixed uniformly, and then aluminum sol nitric acid solution containing a pore-expanding agent is added to be kneaded uniformly continuously.
Kneading, extruding to form cylindrical shape, drying at 120deg.C for 8 hr, and calcining at 550deg.C for 4 hr to obtain micro-mesoporous molecular sieve carrier M-5 with specific surface area and pore size distribution shown in Table 2.
6.73g of barium nitrate and 16.65g of calcium nitrate tetrahydrate are weighed and added into 120ml of distilled water to prepare auxiliary agent impregnating solution, then 340.00g of micro-mesoporous molecular sieve carrier M-5 is impregnated for 15 hours at normal temperature, after impregnation, the molecular sieve carrier is dried for 8 hours at 110 ℃, and baked for 8 hours at 380 ℃ to obtain 347.89g of barium-calcium modified molecular sieve carrier.
Then weighing 191.8g of copper nitrate hexahydrate, adding 92.19g of nickel nitrate hexahydrate into 200ml of distilled water to prepare an impregnating solution, impregnating the barium-calcium modified molecular sieve carrier for 18 hours at normal temperature, drying for 5 hours at 130 ℃ after impregnation, and roasting for 6 hours at 480 ℃ to obtain 434.74g of desulfurization adsorbent 5.
The desulfurization adsorbent 5 mainly comprises the following components: 14.53wt% of copper oxide, 5.45wt% of nickel oxide, 0.91wt% of barium oxide, 0.91wt% of calcium oxide and 78.2wt% of micro-mesoporous molecular sieve carrier M-5.
The embodiment also provides a deep desulfurization method for the carbon tetra-alkane, which comprises the following steps:
a 30ml fixed bed reactor is adopted, and the fixed bed reactor is filled with desulfurization adsorbent 5;
introducing isobutane raw material into a reactor from the bottom of a 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 space velocity of the volume liquid of the isobutane raw material is 2.0h -1 And analyzing the sulfur content in the isobutane raw material at the outlet of the fixed bed reactor, and stopping the experiment when the sulfur content in the isobutane raw material at the outlet of the fixed bed reactor reaches 1mg/kg, considering that the desulfurization adsorbent penetrates. The time from the initial reaction time to the outlet sample sulfur mass fraction of the desulfurization adsorbent higher than 1mg/kg is the penetration time of the desulfurization adsorbent. And in the penetrating time, the mass fraction of the sulfur element adsorbed on the desulfurization adsorbent is the penetrating sulfur capacity of the adsorbent. The breakthrough time was 43 hours and the reactivity of desulfurization adsorbent 5 is shown in Table 3.
Example 6:
the embodiment provides a method for preparing a desulfurization adsorbent, which comprises the following steps:
200g of alumina-containing 20% alumina sol was weighed in a beaker, and 12.0g of 68% nitric acid was added to the alumina sol to obtain an alumina sol nitric acid solution; 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 mixed uniformly, and then aluminum sol nitric acid solution containing a pore-expanding agent is added to be kneaded uniformly continuously.
Kneading, extruding to form cylindrical shape, drying at 120deg.C for 8 hr, and calcining at 500deg.C for 4 hr to obtain micro-mesoporous molecular sieve carrier M-6 with specific surface area and pore size distribution shown in Table 2.
6.48g of barium nitrate and 64.07g of calcium nitrate tetrahydrate are weighed and added into 150ml of distilled water to prepare auxiliary agent impregnating solution, then 340.00g of micro-mesoporous molecular sieve carrier M-6 is impregnated for 16 hours at normal temperature, the impregnated material is dried for 10 hours at 110 ℃, and baked for 9 hours at 480 ℃ to obtain 358.99g of barium-calcium modified molecular sieve carrier.
Then 46.13g of copper nitrate hexahydrate and 177.37g of nickel nitrate hexahydrate are weighed and added into 200ml of distilled water to prepare impregnating solution, then the barium-calcium modified molecular sieve carrier is impregnated for 20 hours at normal temperature, and after the impregnation, the molecular sieve carrier is dried for 8 hours at 130 ℃ and baked for 7 hours at 480 ℃ to obtain 419.75g of desulfurization adsorbent 6.
The desulfurization adsorbent 6 mainly comprises the following components: 3.62 weight percent of copper oxide, 10.86 weight percent of nickel oxide, 0.90 weight percent of barium oxide, 3.62 weight percent of calcium oxide and 81 weight percent of micro-mesoporous molecular sieve carrier M-6.
The embodiment also provides a deep desulfurization method for the carbon tetra-alkane, which comprises the following steps:
a 30ml fixed bed reactor is adopted, and the fixed bed reactor is filled with desulfurization adsorbent 6;
introducing isobutane raw material into a reactor from the bottom of a 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 space velocity of the volume liquid of the isobutane raw material is 2.0h -1 The sulfur content in the isobutane raw material at the outlet of the fixed bed reactor was analyzed, and when the sulfur content in the isobutane raw material at the outlet of the fixed bed reactor reached 1mg/kg, the desulfurization adsorbent was consideredPenetration and stopping the experiment. The time from the initial reaction time to the outlet sample sulfur mass fraction of the desulfurization adsorbent higher than 1mg/kg is the penetration time of the desulfurization adsorbent. And in the penetrating time, the mass fraction of the sulfur element adsorbed on the desulfurization adsorbent is the penetrating sulfur capacity of the adsorbent. The breakthrough time was 46 hours and the reactivity of desulfurization adsorbent 6 is shown in Table 3.
Comparative example 1:
this comparative example provides a method for preparing a desulfurization adsorbent comprising the steps of:
240g of an alumina-containing 25% alumina sol was weighed in a beaker, 14.0g of oxalic acid was added to the alumina sol and mixed well, 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 aluminum sol oxalic acid solution is added to continuously and uniformly knead.
Kneading and extruding to form 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.
12.63g of barium nitrate and 31.24g of calcium nitrate tetrahydrate are weighed and added into 100ml of distilled water to prepare auxiliary agent impregnating solution, then 360g of microporous molecular sieve carrier N-1 is impregnated for 20 hours at normal temperature, the impregnated microporous molecular sieve carrier is dried for 8 hours at 110 ℃ and baked for 3 hours at 530 ℃ to obtain 374.81g of barium-calcium modified molecular sieve carrier.
Then 89.98g of copper nitrate hexahydrate and 100.91g of nickel nitrate hexahydrate are weighed and added into 200ml of distilled water to prepare impregnating solution, then the barium-calcium modified molecular sieve carrier is impregnated for 20 hours at normal temperature, and the impregnated carrier is dried for 10 hours at 110 ℃ and baked for 3 hours at 530 ℃ to obtain the desulfurization adsorbent D-1.
The desulfurization adsorbent D-1 mainly comprises the following components: 6.88wt% of copper oxide, 6.02wt% of nickel oxide, 1.72wt% of barium oxide, 1.72wt% of calcium oxide and 83.66wt% of molecular sieve carrier N-1.
Desulfurization experiments with this desulfurization adsorbent D-1 were the same as in example 1.
Comparative example 2:
this comparative example provides a method for preparing a desulfurization adsorbent comprising the steps of:
the preparation process of the micro mesoporous molecular sieve carrier M-1 is the same as that of the example 1.
12.63g of barium nitrate and 31.24g of calcium nitrate tetrahydrate are weighed and added into 100ml of distilled water to prepare auxiliary agent impregnating solution, then 360g of micro-mesoporous molecular sieve carrier M-1 is impregnated for 20 hours at normal temperature, the impregnated material is dried for 8 hours at 110 ℃ and baked for 3 hours at 530 ℃ to obtain 374.81g of barium-calcium modified molecular sieve carrier.
Then 89.98g of copper nitrate trihydrate is weighed and added into 120ml of distilled water to prepare impregnating solution, then the barium-calcium modified molecular sieve carrier is impregnated for 20 hours at normal temperature, and after the impregnation, the mixture is dried for 10 hours at 110 ℃ and baked for 3 hours at 530 ℃ to obtain 404.47g of desulfurization adsorbent D-2.
The desulfurization adsorbent D-2 mainly comprises the following components: 7.32wt% of copper oxide, 1.83wt% of barium oxide, 1.83wt% of calcium oxide and 89.02wt% of micro-mesoporous molecular sieve carrier M-1.
Desulfurization experiments with this desulfurization adsorbent D-2 were the same as in example 1.
Comparative example 3:
this comparative example provides a method for preparing a desulfurization adsorbent comprising the steps of:
the preparation process of the micro mesoporous molecular sieve carrier M-1 is the same as that of the example 1.
12.63g of barium nitrate and 31.24g of calcium nitrate tetrahydrate are weighed and added into 100ml of distilled water to prepare auxiliary agent impregnating solution, then 360g of micro-mesoporous molecular sieve carrier M-1 is impregnated for 20 hours at normal temperature, the impregnated material is dried for 8 hours at 110 ℃ and baked for 3 hours at 530 ℃ to obtain 374.81g of barium-calcium modified molecular sieve carrier.
Then 100.91g of nickel nitrate hexahydrate is weighed and added into 200ml of distilled water to prepare impregnating solution, then the barium-calcium modified molecular sieve carrier is impregnated for 20 hours at normal temperature, and after the impregnation, the mixture is dried for 10 hours at 110 ℃ and baked for 3 hours at 530 ℃ to obtain 400.74g of desulfurization adsorbent D-3.
The desulfurization adsorbent D-3 mainly comprises the following components: 6.47wt% of nickel oxide, 1.85wt% of calcium oxide, 1.85wt% of barium oxide and 89.83wt% of micro-mesoporous molecular sieve carrier M-1.
Desulfurization experiments with this desulfurization adsorbent D-3 were the same as in example 1.
Table 2 below shows the specific surface area and pore size distribution of the micro-mesoporous molecular sieve carrier, and Table 3 shows the results of evaluating the performance of the desulfurization adsorbent.
Table 2:
table 3:
from the characterization data in table 2, it can be seen that the total pores Rong Mingxian of the adsorbent added with the pore-forming agent are increased, and the average pore diameter of the mesopores is obviously higher than that of the adsorbent without the pore-forming agent, which indicates that the addition of the pore-forming agent can obviously introduce mesopores into the adsorbent system.
From the experimental data in table 3, it can be seen that: the desulfurization performance of the desulfurization adsorbent added with the copper, nickel, barium and calcium is obviously higher than that of the desulfurization adsorbent added with three or two metals, the desulfurization adsorbent added with the four metals has longer penetration time and higher sulfur capacity, and the penetration sulfur capacity of the desulfurization adsorbent can reach more than 4.7 percent.
Claims (14)
1. A desulfurization adsorbent comprising, in weight percent, 100 wt%:
60-85% of micro mesoporous molecular sieve carrier;
2-16 wt% of copper oxide;
1-18 wt% of nickel oxide;
0.2-5.0 wt% of barium oxide;
0.2-5.0 wt% of calcium oxide;
wherein the aperture distribution of the micro-mesoporous molecular sieve carrier is 1-15 nm, the total pore volume is 0.3-0.5 ml/g, and the specific surface area is 500-550 m 2 /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 pore diameter distribution is 8-15 nm, and the mesoporous volume accounts for 20% -60% of the total pore volume;
the preparation method of the micro-mesoporous molecular sieve carrier comprises the following steps:
adding organic acid and/or inorganic acid into the aluminum sol to obtain an aluminum sol acidic solution, and then dissolving a pore-expanding agent into the aluminum sol acidic 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, and then adding aluminum sol acid liquor containing a pore-expanding agent for continuous uniform kneading; the mass ratio of the pore expanding agent to the aluminum sol is 1: (4-20); in the aluminum sol, the mass content of aluminum oxide is 20-25 wt%, and the pore-expanding agent comprises polyvinyl alcohol; the mass ratio of the pore expanding agent to the molecular sieve powder is 1: (10-50), wherein the mass ratio of the molecular sieve powder to the carboxymethyl cellulose is (10-30): 1, a step of;
the molecular sieve carrier with the micro-mesoporous structure is obtained through extrusion, molding, drying and roasting.
2. The desulfurization adsorbent of claim 1, wherein the desulfurization adsorbent comprises, in weight percent 100 wt%:
70-85% of micro mesoporous molecular sieve carrier;
2-15 wt% of copper oxide;
2-12 wt% of nickel oxide;
0.3-3.5 wt% of barium oxide;
0.4-3.7 wt% of calcium oxide.
3. The method for producing a desulfurization adsorbent as claimed in claim 1 or 2, comprising the steps of:
mixing soluble barium salt and soluble calcium salt, adding water to prepare a first impregnating solution, impregnating a micro-mesoporous molecular sieve carrier in the first impregnating solution, and drying and roasting after impregnation to obtain a barium-calcium modified carrier;
mixing soluble copper salt and soluble nickel salt, adding water to prepare a second impregnating solution, impregnating a barium-calcium modified carrier in the second impregnating solution, drying and roasting after impregnation to obtain the desulfurization adsorbent.
4. A method of preparation according to claim 3, 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.
5. The method of claim 4, wherein the soluble barium salt, the soluble calcium salt, the soluble copper salt, and the soluble nickel salt are nitrate salts thereof.
6. The preparation method of claim 3, wherein the temperature of the first impregnating solution is normal temperature, and the impregnating time is 12-20 h; the temperature of drying after soaking is 90-140 ℃, and the time of drying is 4-10 hours; the roasting temperature after drying is 350-550 ℃ and the roasting time is 4-9 h.
7. The preparation method of claim 3, wherein the temperature of the second impregnating solution is normal temperature, and the impregnating time is 12-20 h; the temperature of drying after soaking is 90-140 ℃, and the time of drying is 4-10 hours; the roasting temperature after drying is 350-550 ℃ and the roasting time is 4-9 h.
8. A production method according to claim 3, wherein the organic acid comprises oxalic acid and/or citric acid; the inorganic acid includes nitric acid and/or hydrochloric acid.
9. The method of claim 3, wherein the molecular sieve powder comprises one or more of NaY molecular sieve raw powder, naX molecular sieve raw powder, ZSM-5 molecular sieve raw powder, and MCM-41 molecular sieve raw powder.
10. The method according to claim 3, wherein the amount of the organic acid and/or the inorganic acid is 2wt% to 35wt% of the pore-expanding agent.
11. The preparation method according to claim 3, wherein the temperature at which drying is performed after extrusion molding is 90-140 ℃ and the drying time is 4-10 hours; the roasting temperature after drying is 350-550 ℃, and the roasting time is 4-9 h.
12. A method for deep desulfurization of a carbon tetraalkoxide comprising the steps of:
using a fixed bed reactor packed with the desulfurization adsorbent according to claim 1 or 2;
introducing the carbon tetra-alkane into a fixed bed reactor for desulfurization treatment to obtain the desulfurized carbon tetra-alkane.
13. The method of claim 12, wherein in the desulfurization process, the reaction temperature is 0-80 ℃, the reaction pressure is 0.4-2.5 MPa, and the volume liquid space velocity of the tetra-alkane is 0.2-5.0 h -1 。
14. The method of claim 13, wherein in the desulfurization process, the reaction temperature is 10-70 ℃, the reaction pressure is 0.6-2.0 MPa, and the volume liquid space velocity of the tetra-alkane is 0.5-4.0 h -1 。
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