CN113797881B - Petroleum and petrochemical waste gas adsorbent and preparation method and application thereof - Google Patents

Petroleum and petrochemical waste gas adsorbent and preparation method and application thereof Download PDF

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CN113797881B
CN113797881B CN202110975699.3A CN202110975699A CN113797881B CN 113797881 B CN113797881 B CN 113797881B CN 202110975699 A CN202110975699 A CN 202110975699A CN 113797881 B CN113797881 B CN 113797881B
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reaction kettle
sodium silicate
parts
gas adsorbent
petrochemical
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CN113797881A (en
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郑善
郑星
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Tianjin Langhua Technology Development Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28047—Gels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28076—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being more than 1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores

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  • General Chemical & Material Sciences (AREA)
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Abstract

The invention relates to a petroleum and petrochemical waste gas adsorbent, and a preparation method and application thereof. The petroleum and petrochemical waste gas adsorbent of the invention comprises: silicon aerogel powder, an aluminum-based additive, a viscose and water. The preparation method comprises the following steps: uniformly mixing silicon aerogel powder with an alcohol solvent, and then adding an aluminum-based additive for uniform mixing; and finally, adding the viscose and water, uniformly mixing, kneading into clusters, extruding strips, cutting into small sections, rolling into spheres with the diameter of 1-3 mm, and roasting to prepare the petroleum and petrochemical waste gas adsorbent. Compared with active carbon, the petroleum and petrochemical waste gas adsorbent disclosed by the invention has the advantages of high temperature resistance, good water resistance, strong adsorption capacity, capability of being recycled for multiple times, safety and environmental friendliness.

Description

Petroleum and petrochemical waste gas adsorbent and preparation method and application thereof
Technical Field
The invention relates to the field of petroleum and petrochemical industry, in particular to a petroleum and petrochemical waste gas adsorbent and a preparation method and application thereof.
Background
With the rapid development of national socioeconomic performance, the requirements of the country on environmental protection are further improved. How to economically and reasonably treat the tail gas is an important direction of environmental protection, and accords with the energy structure and development strategy of China.
Petrochemical enterprises are one of the main emission sources of Volatile Organic Compounds (VOCs), and the main emission points are as follows: the tail gas, waste gas, crude oil and product tank area exhaust gas, middle tank area exhaust gas, sewage treatment plant exhaust gas and the like of the production process are characterized in that the exhaust points are multiple and dispersed, the fluctuation of the exhaust concentration range is large, and the composition of VOCs is complex.
The method has the advantages that the problem that a large amount of VOCs (volatile organic compounds) are required to be treated is faced in the production process of the petrochemical industry, the components of the VOCs in the petrochemical industry are complex, the existing treatment process is complex, the risk is high in the process, and a large lifting space is reserved from an ideal safe environment-friendly target.
The current common method is that the concentration of the VOCs waste gas is reduced by washing, catalytic combustion and other methods, and then the residual waste gas is adsorbed and collected by an adsorbent. For the adsorption saturated adsorbent, some of the adsorbents try to desorb and recover the components meeting the conditions, and the rest of the adsorbents can take heavy gold to entrust the professional company to treat dangerous waste products.
The activated carbon has the advantages of low price, large adsorption capacity and wide application range, and is still one of the most commonly used adsorbents in the treatment of petrochemical VOCs waste gas. However, due to the limitations of the materials, the following serious drawbacks exist:
Poor high temperature resistance and flammability
The temperature of the activated carbon can rise in the adsorption process, and when the temperature of the adsorption bed is higher than a set value (generally 83 ℃), an automatic alarm can be started, and a cooling system is started to cool. Therefore, the VOCs waste gas to be adsorbed is generally controlled below 40 ℃, and the temperature of some VOCs waste gas with initial temperature higher than 40 ℃ is reduced.
The active carbon adsorption has very strict requirement on temperature, and has light weight to affect the adsorption efficiency and heavy weight to cause serious safety accidents, such as spontaneous combustion explosion, etc.
Difficult to desorb
A considerable part of valuable components in the adsorbate of the adsorbent need to be recovered and utilized after desorption. In the same way, one of the common ways of desorbing the adsorbent is to raise the temperature for desorption, and the temperature of the activated carbon cannot be raised too high due to the limitation of the material characteristics of the activated carbon, otherwise, the activated carbon has a risk of fire and explosion. This results in some substances with high desorption temperature requirements being unable to be desorbed smoothly, and the recovery effect of the effective substances is not ideal.
High use cost
Although the unit price of the activated carbon is low, the cost of the integrated use is not low. Most activated carbon adsorbents are "disposable" consumables and require periodic replacement (typically one month in the petrochemical industry). Each time a shutdown is required for replacing the carbon bed, the shutdown causes huge economic loss to enterprises. The amount of each replacement is not low, and the long-term accumulation is still a great expense which cannot be ignored.
The cost of carbon replacement is removed, the treatment cost of the waste carbon is quite high, and the waste carbon is required to be treated by a professional hazardous waste treatment company. It is known that the market price for treating 1 ton of waste carbon requires 4000 RMB or more. The above costs add up, already placing a significant financial burden on the enterprise.
Pollution to environment
The disposal of dangerous waste products is always carried out without burning and landfill. Although professional hazardous waste disposal companies are conducted on the premise of meeting the standards, the hazardous waste disposal companies still inevitably have influence on the environment.
Based on the defects, the related experts and practitioners are searching for a new material which overcomes the defects and has better performance while improving the performance of the activated carbon.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a petroleum and petrochemical waste gas adsorbent and a preparation method and application thereof. Compared with active carbon, the petroleum and petrochemical waste gas adsorbent disclosed by the invention has the advantages of high temperature resistance, good water resistance, strong adsorption capacity, capability of being recycled for multiple times, safety and environmental friendliness.
The invention aims to provide a petroleum and petrochemical waste gas adsorbent, which comprises the following components in parts by weight:
30-50 parts of silicon aerogel powder;
9-25 parts of aluminum-based additive;
8-16 parts of mucilage;
And 20-38 parts of deionized water.
Preferably, the specific surface area of the silicon aerogel powder is 480-800 m 2/g; the pore volume is 1.6-2.5 ml/g; the pore diameter is in the range of 1-30nm.
The preparation method of the silicon aerogel powder comprises the following steps:
(1) Preparation of a Mixed solution of a silicon Source and a solvent
Loading sodium silicate with the modulus of 2.5-2.8 into a reaction kettle, adding deionized water with the mass 5 times of that of the sodium silicate for dilution, stirring the reaction kettle for 30 minutes at the speed of 240 revolutions per minute, and filtering the mixture through a 200-mesh sieve to obtain a sodium silicate solution;
(2) Sol-gel
Adding water into oxalic acid, diluting the concentration to 20-25 mol/L, adding aluminum oxalate and yttrium oxalate into the oxalic acid, uniformly mixing, and adding into the sodium silicate solution obtained in the step (1) in a mode of submerged injection (simultaneous injection of a plurality of metering pumps); the whole feeding time is controlled to be 5-10 minutes, the stirring speed is 300-400 rpm, and the pH value of the sodium silicate solution is controlled to be 1.5-3.0, so that sol is obtained; the molar ratio of the aluminum oxalate to the yttrium oxalate is 100 in terms of oxide: 3, a step of; the molar ratio of the oxide of aluminum oxalate to the silicon oxide in sodium silicate is 3:100;
(3) Gel
Adding deionized water into sodium hydroxide or ammonia water to dilute to pH value of 11, and adding into a reaction kettle in a spraying manner; the materials in the reaction kettle are rapidly stirred at the speed of 2000 rpm while spraying, and when the pH value of the materials in the reaction kettle is 5.5, the spraying is stopped to obtain gel;
(4) Aging
Continuously stirring the materials in the reaction kettle for 15 hours at the speed of 20 revolutions per minute, aging the materials in the reaction kettle, and controlling the temperature of the materials in the reaction kettle to be 20 ℃;
(5) Solvent displacement
Continuously stirring for 90 minutes in the reaction kettle, and simultaneously adding n-hexane which is a displacement solvent and has the same volume as the aged materials in the reaction kettle in the step (4) to displace residual water;
(6) Surface modification
Continuously stirring in the reaction kettle, and continuously adding the coupling agent dimethoxy dimethyl silane with the same volume as the aged materials in the reaction kettle in the step (4); stirring for 80 minutes to obtain a silicon aerogel precursor coated with a replacement solvent n-hexane and a coupling agent dimethoxy dimethyl silane;
(7) Drying
And (3) putting the silicon aerogel precursor into a drying kettle, filling nitrogen into the drying kettle to remove oxygen until the oxygen content in the drying kettle is less than 3%, then carrying out microwave vacuum drying on materials in the drying kettle for 70 minutes at the microwave frequency of 2450MHz, and drying at the temperature of 100 ℃ under the negative pressure of 0.1MPa in the drying kettle to obtain the solid powdery silicon aerogel.
Preferably, the aluminum-based additive is one or a combination of aluminum hydroxide, pseudo-boehmite and metaaluminate monohydrate.
The aperture range of the aluminum-based additive after roasting is approximately between 0.2 nanometers and 10 nanometers, which is beneficial to the generation of small apertures in products, can further enrich the aperture range of the adsorbent, increase the specific surface area of the adsorbent and the acidity of the adsorbent, and improve the adsorption effect on alkaline gas.
Preferably, the adhesive comprises the following raw materials in parts by weight:
20-30 parts of sodium silicate;
15-25 parts of potassium silicate;
30-50 parts of distilled water;
15-25 parts of silica sol;
3-6 parts of a silane coupling agent;
15-20 parts of magnesium hydroxide and/or magnesium oxide.
In the adhesive, the matrix is sodium silicate and potassium silicate; the addition of the silica sol silane, the coupling agent, the magnesium hydroxide and/or the magnesium oxide has a synergistic effect, so that the adhesive has stronger adhesive property, toughness and water resistance.
The adhesive adopts an inorganic special formula, and aims to meet higher temperature while granulating to maintain due strength so as to realize the requirement of high-temperature desorption;
Preferably, the silane coupling agent is one or a combination of perfluorooctyl trimethoxy silane, perfluorooctyl triethoxy silane and perfluorodecyl trimethoxy silane;
The solid content of the silica sol is 25-32%.
Preferably, the preparation method of the silica sol comprises the following steps:
(1) Preparation of a Mixed solution of a silicon Source and a solvent
Loading sodium silicate with the modulus of 3.5 into a reaction kettle, adding deionized water with the mass of 2 times of that of the sodium silicate for dilution, stirring the reaction kettle for 30 minutes at the speed of 100 revolutions per minute, and filtering the mixture through a 200-mesh sieve to obtain a sodium silicate solution;
(2) Sol-gel
Taking sulfuric acid, regulating the sulfuric acid to 10 mol/L by using deionized water, adding zirconium sulfate and cerium sulfate into the sulfuric acid, uniformly mixing, and adding the mixture into the sodium silicate solution obtained in the step (1) in a spraying mode; the materials in the reaction kettle are rapidly stirred at the speed of 1500 rpm while spraying, the pH value of the sodium silicate solution is controlled to be 2.0, and the spraying time is controlled to be 80 minutes, so that sol is obtained; the molar ratio of the zirconium sulfate to the cerium sulfate is 100 in terms of oxide: 4, a step of; the mol ratio of the oxide in the zirconium sulfate to the silicon oxide in the sodium silicate is 3:100;
(3) Solvent displacement
Adding a displacement solvent acetone with the same volume as the ageing materials in the reaction kettle in the step (3) into the reaction kettle to displace residual water silica sol; concentrating the silica sol until the solid content is about 25-35%; the concentration can be carried out by adopting a common ultrafiltration membrane concentration method.
Preferably, the preparation method of the adhesive comprises the following steps:
Uniformly stirring all the raw materials in the adhesive, then adding an acid solution to enable the pH value to be 7-9, stirring for 90-100min, and heating to 80-90 ℃ to obtain the adhesive;
If the pH value of the adhesive is too alkaline, the water resistance of the adhesive is reduced, the pH value is between 7 and 9, and the water resistance effect is good.
The acid solution is one or a solution prepared by combining nitric acid, hydrochloric acid and acetic acid; the weight ratio of the acid to the water in the acid solution is 4-9:1.
The second object of the invention is to provide a preparation method of the petroleum and petrochemical waste gas adsorbent, which comprises the following steps: uniformly mixing silicon aerogel powder with an alcohol solvent, and then adding an aluminum-based additive for uniform mixing; and finally, adding the viscose and water, uniformly mixing, kneading into clusters, extruding strips, cutting into small sections, rolling into spheres with the diameter of 1-3 mm, and roasting to prepare the petroleum and petrochemical waste gas adsorbent.
Preferably, the mass of the alcohol solvent is equal to that of the silicon aerogel powder, and the alcohol solvent is one or more of methanol, propanol and ethanol.
Preferably, the pressure during extrusion is 10-15MPa; the roasting temperature is 450-750 ℃.
Preferably, the compressive strength of the petroleum and petrochemical waste gas adsorbent is equal to or greater than 0.098MPa; the average pore diameter is 3-5nm.
It is a further object of the present invention to provide the use of a petrochemical exhaust gas adsorbent for the adsorption of petrochemical exhaust gas.
The beneficial effects are that:
The base material of the adsorbent of the invention is Si (silicon), A1 grade is nonflammable and can bear high temperature of thousands of DEG C. The adsorbent has no fear of heating pressure during desorption, can freely realize the desorption of active ingredients in various temperature sections, and can improve the recycling rate of VOCs to a new level.
The adsorbent of the invention can repeatedly regenerate VOCs with recovery value for many times, and is not consumed as a container. Even for VOCs without recovery value, the adsorbent with the same quality can adsorb waste gas which is several times that of active carbon, so that firstly, the period for replacing the adsorbent can be prolonged, the loss caused by shutdown and production stoppage is reduced, and secondly, the expenditure for treating dangerous waste products can be greatly reduced.
The adsorbent of the invention has larger adsorption capacity than that of activated carbon, less adsorbent is needed for adsorbing the same amount of VOCs waste gas, and the pressure on the environment is reduced when hazardous waste is treated.
The adsorbent of the invention has smooth surface and can not crack or peel after being used for a plurality of times.
The existing inorganic adhesive has excellent high-temperature resistance, but has poor water resistance, large brittleness and no impact resistance, and the adhesive has good bonding strength, good water resistance, good toughness and very good use value.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
Example 1
The preparation method of the silicon aerogel powder comprises the following steps:
(1) Preparation of a Mixed solution of a silicon Source and a solvent
Loading sodium silicate with the modulus of 2.5 into a reaction kettle, adding deionized water with the mass 5 times of that of the sodium silicate for dilution, stirring the reaction kettle for 30 minutes at the speed of 240 revolutions per minute, and filtering the mixture through a 200-mesh sieve to obtain a sodium silicate solution;
(2) Sol-gel
Adding water into oxalic acid, diluting the concentration to 21 mol/L, adding aluminum oxalate and yttrium oxalate into the oxalic acid, uniformly mixing, and adding into the sodium silicate solution obtained in the step (1) in a mode of submerged injection (simultaneous injection of a plurality of metering pumps); the whole feeding time is controlled to be 10 minutes, the stirring speed is 400 rpm, and the pH value of the sodium silicate solution is controlled to be 1.8, so that sol is obtained; the molar ratio of the aluminum oxalate to the yttrium oxalate is 100 in terms of oxide: 3, a step of; the molar ratio of the oxide of aluminum oxalate to the silicon oxide in sodium silicate is 3:100;
(3) Gel
Adding deionized water into sodium hydroxide or ammonia water to dilute to pH value of 11, and adding into a reaction kettle in a spraying manner; the materials in the reaction kettle are rapidly stirred at the speed of 2000 rpm while spraying, and when the pH value of the materials in the reaction kettle is 5.5, the spraying is stopped to obtain gel;
(4) Aging
Continuously stirring the materials in the reaction kettle for 15 hours at the speed of 20 revolutions per minute, aging the materials in the reaction kettle, and controlling the temperature of the materials in the reaction kettle to be 20 ℃;
(5) Solvent displacement
Continuously stirring for 90 minutes in the reaction kettle, and simultaneously adding n-hexane which is a displacement solvent and has the same volume as the aged materials in the reaction kettle in the step (4) to displace residual water;
(6) Surface modification
Continuously stirring in the reaction kettle, and continuously adding the coupling agent dimethoxy dimethyl silane with the same volume as the aged materials in the reaction kettle in the step (4); stirring for 80 minutes to obtain a silicon aerogel precursor coated with a replacement solvent n-hexane and a coupling agent dimethoxy dimethyl silane;
(7) Drying
And (3) putting the silicon aerogel precursor into a drying kettle, filling nitrogen into the drying kettle to remove oxygen until the oxygen content in the drying kettle is less than 3%, then carrying out microwave vacuum drying on materials in the drying kettle for 70 minutes at the microwave frequency of 2450MHz, and drying at the temperature of 100 ℃ under the negative pressure of 0.1MPa in the drying kettle to obtain the solid powdery silicon aerogel.
The specific surface area of the prepared silicon aerogel powder is 650 m 2/g; the pore volume is 1.8ml/g, the pore diameter is in the range of 1-30nm, and the average pore diameter is 12nm.
Example 2
The preparation method of the silicon aerogel powder comprises the following steps:
(1) Preparation of a Mixed solution of a silicon Source and a solvent
Loading sodium silicate with the modulus of 2.7 into a reaction kettle, adding deionized water with the mass 5 times of that of the sodium silicate for dilution, stirring the reaction kettle for 30 minutes at the speed of 240 revolutions per minute, and filtering the mixture through a 200-mesh sieve to obtain a sodium silicate solution;
(2) Sol-gel
Taking oxalic acid, adding water, diluting the concentration to 20mol/L, adding aluminum oxalate and yttrium oxalate into the oxalic acid, uniformly mixing, and adding the mixture into the sodium silicate solution obtained in the step (1) in a mode of submerged injection (simultaneous injection of a plurality of metering pumps); the whole feeding time is controlled to be 10 minutes, the stirring speed is 300 revolutions per minute, and the pH value of the sodium silicate solution is controlled to be 3.0, so that sol is obtained; the molar ratio of the aluminum oxalate to the yttrium oxalate is 100 in terms of oxide: 3, a step of; the molar ratio of the oxide of aluminum oxalate to the silicon oxide in sodium silicate is 3:100;
(3) Gel
Adding deionized water into sodium hydroxide or ammonia water to dilute to pH value of 10.5, and adding into a reaction kettle in a spraying manner; the materials in the reaction kettle are rapidly stirred at the speed of 2500 rpm while spraying, and when the pH value of the materials in the reaction kettle is 6, the spraying is stopped to obtain gel;
(4) Aging
Continuously stirring the materials in the reaction kettle at the speed of 35 rpm for 16 hours, aging the materials in the reaction kettle, and controlling the temperature of the materials in the reaction kettle to be 22 ℃;
the remaining process conditions were the same as in example 1.
The specific surface area of the prepared silicon aerogel powder is 480 m 2/g; the pore volume is 2.4ml/g, the pore diameter is in the range of 1-30nm, and the average pore diameter is 15nm.
Example 3
The preparation method of the silicon aerogel powder comprises the following steps:
(1) Preparation of a Mixed solution of a silicon Source and a solvent
Loading sodium silicate with the modulus of 2.8 into a reaction kettle, adding deionized water with the mass 5 times of that of the sodium silicate for dilution, stirring the reaction kettle for 30 minutes at the speed of 240 revolutions per minute, and filtering the mixture through a 200-mesh sieve to obtain a sodium silicate solution;
(2) Sol-gel
Taking oxalic acid, adding water, diluting the concentration to 25mol/L, adding aluminum oxalate and yttrium oxalate into the oxalic acid, uniformly mixing, and adding the mixture into the sodium silicate solution obtained in the step (1) in a mode of submerged injection (simultaneous injection of a plurality of metering pumps); the whole feeding time is controlled to be 5 minutes, the stirring speed is 350 revolutions per minute, and the pH value of the sodium silicate solution is controlled to be 2.0, so that sol is obtained; the molar ratio of the aluminum oxalate to the yttrium oxalate is 100 in terms of oxide: 3, a step of; the molar ratio of the oxide of aluminum oxalate to the silicon oxide in sodium silicate is 3:100;
(3) Gel
Adding deionized water into sodium hydroxide or ammonia water to dilute to pH value of 11, and adding into a reaction kettle in a spraying manner; the materials in the reaction kettle are rapidly stirred at 2100 rpm while spraying, and when the pH value of the materials in the reaction kettle is 5, the spraying is stopped to obtain gel;
(4) Aging
Continuously stirring the materials in the reaction kettle at the speed of 25 revolutions per minute for 17 hours, aging the materials in the reaction kettle, and controlling the temperature of the materials in the reaction kettle to be 18 ℃;
the remaining process conditions were the same as in example 1.
The specific surface area of the prepared silicon aerogel powder is 530 m 2/g; the pore volume is 2.0ml/g, the pore diameter is in the range of 1-30nm, and the average pore diameter is 13nm.
Example 4
The adhesive comprises the following raw materials in parts by weight:
25 parts of sodium silicate;
20 parts of potassium silicate;
38 parts of distilled water;
19 parts of silica sol;
3 parts of perfluorooctyl trimethoxy silane;
magnesium hydroxide and magnesium oxide 15 parts, wherein 10 parts of magnesium hydroxide and 5 parts of magnesium oxide.
The solid content of the silica sol was 30%.
The preparation method of the silica sol comprises the following steps:
(1) Preparation of a Mixed solution of a silicon Source and a solvent
Loading sodium silicate with the modulus of 3.5 into a reaction kettle, adding deionized water with the mass of 2 times of that of the sodium silicate for dilution, stirring the reaction kettle for 30 minutes at the speed of 100 revolutions per minute, and filtering the mixture through a 200-mesh sieve to obtain a sodium silicate solution;
(2) Sol-gel
Taking sulfuric acid, regulating the sulfuric acid to 10 mol/L by using deionized water, adding zirconium sulfate and cerium sulfate into the sulfuric acid, uniformly mixing, and adding the mixture into the sodium silicate solution obtained in the step (1) in a spraying mode; the materials in the reaction kettle are rapidly stirred at the speed of 1500 rpm while spraying, the pH value of the sodium silicate solution is controlled to be 2.0, and the spraying time is controlled to be 80 minutes, so that sol is obtained; the molar ratio of the zirconium sulfate to the cerium sulfate is 100 in terms of oxide: 4, a step of; the mol ratio of the oxide in the zirconium sulfate to the silicon oxide in the sodium silicate is 3:100;
(3) Solvent displacement
Adding a displacement solvent acetone with the same volume as the ageing materials in the reaction kettle in the step (3) into the reaction kettle to displace residual water silica sol; concentrating the silica sol until the solid content is about 30%; the concentration can be carried out by adopting a common ultrafiltration membrane concentration method.
The preparation method of the adhesive comprises the following steps:
uniformly stirring all the raw materials in the adhesive, then adding hydrochloric acid solution, wherein the weight ratio of acid to water in the acid solution is 5:1, enabling the pH value to be 7, stirring for 90min, and heating to 80 ℃ to obtain the adhesive;
Comparative example 1
The raw materials and preparation process of the adhesive of example 4 were the same, except that the pH of the adhesive was 10.
Comparative example 2
The process for preparing the adhesive of example 4 was the same, except that the adhesive material was free of silica sol.
Comparative example 3
The preparation process of the adhesive in example 4 is the same, except that the adhesive raw material does not contain perfluoro octyl trimethoxy silane as a silane coupling agent.
Comparative example 4
The process for preparing the adhesive of example 4 was the same, except that the adhesive raw material was made free of magnesium hydroxide and magnesium oxide.
And (3) angle folding test: the adhesives of the above example 4 and comparative examples 1 to 4 were applied to a wood board having a thickness of 0.5cm, and the wood board was bent until cracks occurred in the adhesive layer, and the angle of the break at this time was recorded, and the results are shown in Table 1.
Table 1 corner test results
Example 5
The adhesive comprises the following raw materials in parts by weight:
22 parts of sodium silicate;
23 parts of potassium silicate;
45 parts of distilled water;
22 parts of silica sol;
4 parts of perfluorooctyl trimethoxy silane;
magnesium hydroxide and magnesium oxide 17 parts, wherein the magnesium hydroxide is 12 parts and the magnesium oxide is 5 parts.
The solid content of the silica sol was 30%.
The silica sol was prepared in the same manner as in example 4.
Example 6
The petroleum and petrochemical waste gas adsorbent comprises the following components in parts by weight:
30 parts of silicon aerogel powder; (silica aerogel powder prepared by example 2)
12 Parts of aluminum-based additive; the aluminum-based additive is aluminum hydroxide
15 Parts of adhesive; (Using the adhesive prepared in example 4)
25 Parts of deionized water.
The preparation method of the petroleum and petrochemical waste gas adsorbent comprises the following steps: uniformly mixing silicon aerogel powder with a methanol solvent, wherein the mass of the ethanol solvent is equal to that of the silicon aerogel powder, and then adding an aluminum-based additive for uniformly mixing; and finally, adding the viscose and water, uniformly mixing, kneading into clusters, extruding strips, cutting into small sections under the pressure of 15MPa, rolling into spheres with the diameter of 2mm, and roasting at the temperature of 550 ℃ to prepare the petroleum and petrochemical waste gas adsorbent.
The compressive strength of the petroleum and petrochemical waste gas adsorbent prepared by the method is 0.11MPa; the average pore diameter was 3nm.
Example 7
The petroleum and petrochemical waste gas adsorbent comprises the following components in parts by weight:
40 parts of silicon aerogel powder; (silica aerogel powder prepared by example 2)
16 Parts of aluminum-based additive; the aluminum-based additive is aluminum hydroxide
10 Parts of adhesive; (Using the adhesive prepared in example 5)
30 Parts of deionized water.
The preparation method of the petroleum and petrochemical waste gas adsorbent comprises the following steps: uniformly mixing silicon aerogel powder with an ethanol solvent, wherein the mass of the ethanol solvent is equal to that of the silicon aerogel powder, and then adding an aluminum-based additive for uniform mixing; and finally, adding the viscose and water, uniformly mixing, kneading into clusters, extruding strips, cutting into small sections under the pressure of 12MPa, rolling into spheres with the diameter of 3mm, and roasting at the temperature of 500 ℃ to prepare the petroleum and petrochemical waste gas adsorbent.
The compressive strength of the petroleum and petrochemical waste gas adsorbent prepared by the method is 0.098MPa; the average pore diameter was 5nm.
Example 8
The petroleum and petrochemical waste gas adsorbent comprises the following components in parts by weight:
35 parts of silicon aerogel powder; (silica aerogel powder prepared by example 2)
22 Parts of aluminum-based additive; the aluminum-based additive is metaaluminate monohydrate
13 Parts of adhesive; (Using the adhesive prepared in example 4)
36 Parts of deionized water.
The preparation method of the petroleum and petrochemical waste gas adsorbent comprises the following steps: uniformly mixing silicon aerogel powder with a methanol solvent, and then adding an aluminum-based additive for uniform mixing; and finally, adding the viscose and water, uniformly mixing, kneading into clusters, extruding strips, cutting into small sections with the pressure of 12 MPa during extruding strips, rolling into spheres with the diameter of 1mm, roasting at the temperature of 700 ℃ to prepare the petroleum and petrochemical waste gas adsorbent.
The compressive strength of the petroleum and petrochemical waste gas adsorbent prepared by the method is 0.11MPa; the average pore diameter was 4nm.
Comparative example 5
The same procedure as in example 6 was followed except that the adhesive of comparative example 1 was used as the adhesive.
The compressive strength of the petroleum and petrochemical waste gas adsorbent prepared by the method is 0.10MPa; the average pore diameter was 3.1nm.
Comparative example 6
The same procedure as in example 6 was followed except that the adhesive of comparative example 2 was used as the adhesive.
The compressive strength of the petroleum and petrochemical waste gas adsorbent prepared by the method is 0.07MPa; the average pore diameter was 7nm.
Comparative example 7
The same preparation method as in example 6 was used, except that the adhesive of comparative example 3 was used.
The compressive strength of the petroleum and petrochemical waste gas adsorbent prepared by the method is 0.08MPa; the average pore diameter was 3.8nm.
Comparative example 8
The same procedure as in example 6 was followed except that the adhesive of comparative example 4 was used as the adhesive.
The compressive strength of the petroleum and petrochemical waste gas adsorbent prepared by the method is 0.065MPa; the average pore diameter was 2.9nm.
Comparative example 9
It is identical to the preparation of example 6, except that no aluminium-based additive is present.
The compressive strength of the petroleum and petrochemical waste gas adsorbent prepared by the method is 0.091MPa; the average pore diameter was 18nm.
Comparative example 10
The same proportion as the adsorbent of example 6 is different in that the preparation method is different in that the silicon aerogel powder, the aluminum-based additive, the mucilage glue and the water are uniformly mixed, and then the alcohol solvent is added for uniform mixing.
The compressive strength of the petroleum and petrochemical waste gas adsorbent prepared by the method is 0.12MPa; the average pore diameter was 4nm.
The petroleum and petrochemical waste gas adsorbents prepared in examples 6 to 7 and comparative examples 5 to 9 were used for adsorbing petroleum and petrochemical waste gas, and the use conditions of the adsorbents were that they were packed into a packed column; the temperature is 30 ℃ during adsorption; the exhaust gas flow was operated according to the pressure requirement of 1.5 MPa.
When the adsorbent is desorbed and utilized, the desorption temperature is 150 ℃.
Comparative example 11
The same operating conditions as described above differ only in that: activated carbon with the aperture range of 1-35nm and the specific surface area of 800 m 2/g is adopted.
The testing method comprises the following steps:
water resistance time: soaking the adsorbent in water, and timing until cracking occurs on the surface of the adsorbent.
Recovery of VOCs: the mass ratio of the desorbed substances in the adsorbent to the substances adsorbed in the adsorbent.
Specific absorption effects are shown in table 2 below: wherein the VOCs in the exhaust gas before the absorption of the adsorbent is 98mg/Nm 3
TABLE 2 absorption Effect of adsorbents
As can be seen from the comparison of the data, if the pH value of the adhesive is too slightly alkaline, the water resistance of the adsorbent is reduced, and when the pH value of the adhesive is between 7 and 9, the water resistance effect is good.
Meanwhile, the adhesive disclosed by the invention is prepared by mutually matching the components, especially the silica sol, the coupling agent and the magnesium oxide and magnesium hydroxide, and the three components are mutually matched, so that the adhesive has relatively good water resistance and toughness. If only common inorganic mucilage glue of sodium silicate or potassium silicate exists, the water-proof time is about 1 hour; and also very brittle, the angle of refraction of the common inorganic adhesive is more than 3 percent.
The silica sol is added into the adhesive provided by the invention, so that the adhesive has a further bonding reinforcing effect, and if the adhesive is replaced by silica aerogel powder, the silica aerogel powder only has a filler effect and does not have a bonding reinforcing effect.
Finally, the adsorbent of the invention also needs to be matched with an aluminum-based additive, so that the pore size range is further enriched, and a better adsorption effect can be achieved.

Claims (7)

1. The petroleum and petrochemical waste gas adsorbent is characterized by comprising the following components in parts by weight:
30-50 parts of silicon aerogel powder;
9-25 parts of aluminum-based additive;
8-16 parts of mucilage;
20-38 parts of deionized water;
the aluminum-based additive is one or a combination of aluminum hydroxide, pseudo-boehmite and metaaluminate monohydrate;
the adhesive comprises the following raw materials in parts by weight:
20-30 parts of sodium silicate;
15-25 parts of potassium silicate;
30-50 parts of distilled water;
15-25 parts of silica sol;
3-6 parts of a silane coupling agent;
15-20 parts of magnesium hydroxide and/or magnesium oxide;
The preparation method of the adhesive comprises the following steps:
Uniformly stirring all the raw materials in the adhesive, then adding an acid solution to enable the pH value to be 7-9, stirring for 90-100min, and heating to 80-90 ℃ to obtain the adhesive;
The preparation method of the petroleum and petrochemical waste gas adsorbent comprises the following steps: uniformly mixing silicon aerogel powder with an alcohol solvent, and then adding an aluminum-based additive for uniform mixing; finally, adding the viscose and water, uniformly mixing, kneading into clusters, extruding strips, cutting into small sections, rolling into spheres with the diameter of 1-3 mm, and roasting to prepare the petroleum and petrochemical waste gas adsorbent;
The preparation method of the silicon aerogel powder used for the petroleum and petrochemical waste gas adsorbent comprises the following steps:
(1) Preparation of a Mixed solution of a silicon Source and a solvent
Loading sodium silicate with the modulus of 2.5-2.8 into a reaction kettle, adding deionized water with the mass 5 times of that of the sodium silicate for dilution, stirring the reaction kettle for 30 minutes at the speed of 240 revolutions per minute, and filtering the mixture through a 200-mesh sieve to obtain a sodium silicate solution;
(2) Sol-gel
Adding water into oxalic acid, diluting the concentration to 20-25 mol/L, adding aluminum oxalate and yttrium oxalate into the oxalic acid, uniformly mixing, and adding into the sodium silicate solution obtained in the step (1) in a submerged injection mode; the whole feeding time is controlled to be 5-10 minutes, the stirring speed is 300-400 rpm, and the pH value of the sodium silicate solution is controlled to be 1.5-3.0, so that sol is obtained; the molar ratio of the aluminum oxalate to the yttrium oxalate is 100 in terms of oxide: 3, a step of; the molar ratio of the oxide of aluminum oxalate to the silicon oxide in sodium silicate is 3:100;
(3) Gel
Adding deionized water into sodium hydroxide or ammonia water to dilute to pH value of 11, and adding into a reaction kettle in a spraying manner; the materials in the reaction kettle are rapidly stirred at the speed of 2000 rpm while spraying, and when the pH value of the materials in the reaction kettle is 5.5, the spraying is stopped to obtain gel;
(4) Aging
Continuously stirring the materials in the reaction kettle for 15 hours at the speed of 20 revolutions per minute, aging the materials in the reaction kettle, and controlling the temperature of the materials in the reaction kettle to be 20 ℃;
(5) Solvent displacement
Continuously stirring for 90 minutes in the reaction kettle, and simultaneously adding n-hexane which is a displacement solvent and has the same volume as the aged materials in the reaction kettle in the step (4) to displace residual water;
(6) Surface modification
Continuously stirring in the reaction kettle, and continuously adding the coupling agent dimethoxy dimethyl silane with the same volume as the aged materials in the reaction kettle in the step (4); stirring for 80 minutes to obtain a silicon aerogel precursor coated with a replacement solvent n-hexane and a coupling agent dimethoxy dimethyl silane;
(7) Drying
Putting a silicon aerogel precursor into a drying kettle, filling nitrogen into the drying kettle to remove oxygen until the oxygen content in the drying kettle is less than 3%, then carrying out microwave vacuum drying on materials in the drying kettle for 70 minutes at a microwave frequency of 2450MHz, and drying at a temperature of 100 ℃ under a negative pressure of 0.1MPa in the drying kettle to obtain solid powdery silicon aerogel;
The preparation method of the silica sol in the viscose comprises the following steps:
(1) Preparation of a Mixed solution of a silicon Source and a solvent
Loading sodium silicate with the modulus of 3.5 into a reaction kettle, adding deionized water with the mass of 2 times of that of the sodium silicate for dilution, stirring the reaction kettle for 30 minutes at the speed of 100 revolutions per minute, and filtering the mixture through a 200-mesh sieve to obtain a sodium silicate solution;
(2) Sol-gel
Taking sulfuric acid, regulating the sulfuric acid to 10 mol/L by using deionized water, adding zirconium sulfate and cerium sulfate into the sulfuric acid, uniformly mixing, and adding the mixture into the sodium silicate solution obtained in the step (1) in a spraying mode; the materials in the reaction kettle are rapidly stirred at the speed of 1500 rpm while spraying, the pH value of the sodium silicate solution is controlled to be 2.0, and the spraying time is controlled to be 80 minutes, so that sol is obtained; the molar ratio of the zirconium sulfate to the cerium sulfate is 100 in terms of oxide: 4, a step of; the mol ratio of the oxide in the zirconium sulfate to the silicon oxide in the sodium silicate is 3:100;
(3) Solvent displacement
Adding a displacement solvent acetone with the same volume as the ageing materials in the reaction kettle in the step (3) into the reaction kettle to displace residual water silica sol; concentrating the silica sol until the solid content is about 25-35%; the concentration can be carried out by adopting a common ultrafiltration membrane concentration method.
2. The petrochemical exhaust gas adsorbent of claim 1, wherein: the specific surface area of the silicon aerogel powder is 480-800 m 2/g; the pore volume is 1.6-2.5 ml/g; the pore diameter is in the range of 1-30nm.
3. The petrochemical exhaust gas adsorbent of claim 1, wherein: the silane coupling agent is one or a combination of perfluorooctyl trimethoxy silane, perfluorooctyl triethoxy silane and perfluorodecyl trimethoxy silane;
The solid content of the silica sol is 25-32%.
4. The petrochemical exhaust gas adsorbent of claim 1, wherein:
The acid solution is one or a solution prepared by combining nitric acid, hydrochloric acid and acetic acid; the weight ratio of the acid to the water in the acid solution is 4-9:1.
5. The petrochemical exhaust gas adsorbent of claim 1, wherein: the mass of the alcohol solvent is equal to that of the silicon aerogel powder, and the alcohol solvent is one or more of methanol, propanol and ethanol.
6. The petrochemical exhaust gas adsorbent of claim 1, wherein: the pressure during extrusion is 10-15MPa; the roasting temperature is 450-750 ℃.
7. Use of a petrochemical flue gas adsorbent according to any one of claims 1 to 4, characterized in that: the adsorbent is used for adsorbing petroleum and petrochemical waste gas.
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WO1998047594A2 (en) * 1997-04-18 1998-10-29 Cabot Corporation Use of aerogels as adsorption agents
GB2342349A (en) * 1998-10-08 2000-04-12 Richard Dudley Shaw Binding refractories
CN1265050A (en) * 1997-05-07 2000-08-30 株式会社宇宙总合研究所 Adhesive, process for preparing same, and method for recovering vapor of hydrocarbon by utilizing condensation by cooling
CN104475059A (en) * 2014-11-28 2015-04-01 中国科学技术大学先进技术研究院 Preparation method of sponge-silicon aerogel composite material
CN107282033A (en) * 2017-06-28 2017-10-24 郑善 It is a kind of to be used for photochemical catalyst that air V OC is handled and preparation method thereof
WO2018049965A1 (en) * 2016-09-14 2018-03-22 周水林 Method for quickly preparing aerogel by using microemulsion as precursor
CN110841592A (en) * 2019-10-31 2020-02-28 上海蓝科石化环保科技股份有限公司 Adsorbent for purifying VOCs waste gas and preparation method and application thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998047594A2 (en) * 1997-04-18 1998-10-29 Cabot Corporation Use of aerogels as adsorption agents
CN1265050A (en) * 1997-05-07 2000-08-30 株式会社宇宙总合研究所 Adhesive, process for preparing same, and method for recovering vapor of hydrocarbon by utilizing condensation by cooling
GB2342349A (en) * 1998-10-08 2000-04-12 Richard Dudley Shaw Binding refractories
CN104475059A (en) * 2014-11-28 2015-04-01 中国科学技术大学先进技术研究院 Preparation method of sponge-silicon aerogel composite material
WO2018049965A1 (en) * 2016-09-14 2018-03-22 周水林 Method for quickly preparing aerogel by using microemulsion as precursor
CN107282033A (en) * 2017-06-28 2017-10-24 郑善 It is a kind of to be used for photochemical catalyst that air V OC is handled and preparation method thereof
CN110841592A (en) * 2019-10-31 2020-02-28 上海蓝科石化环保科技股份有限公司 Adsorbent for purifying VOCs waste gas and preparation method and application thereof

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