阅读说明：本技术 一种用于燃料油的脱硫剂及其制备方法与油品脱硫残余物在道路基层材料中的应用 (Desulfurizing agent for fuel oil, preparation method thereof and application of oil desulfurization residue in road base material ) 是由 车春玲 熊长祥 于 2021-08-10 设计创作，主要内容包括：本申请公开了一种用于燃料油的脱硫剂及其制备方法与油品脱硫残余物在道路基层材料中的应用,属于燃料油脱硫技术领域。所述用于燃料油的脱硫剂的制备方法,包括以下步骤：1)将氧化石墨烯、硅源、碱及表面活性剂混合后反应得到反应液A,将所述反应液A分离后得到反应产物A；2)将步骤1)得到的所述反应产物A分散在有机溶剂A中,加入硅烷偶联剂,反应后得到反应液B,将所述反应液B分离；3)将步骤2)得到的所述反应产物B、还原剂、过渡金属盐分散在去离子水中,并以10-20ml/min的加料速率滴加0.2-0.6M的氢氧化钠溶液,反应后,分离得到所述脱硫剂。(The application discloses a desulfurizer for fuel oil and a preparation method thereof, and application of oil product desulfurization residues in road base materials, belonging to the technical field of fuel oil desulfurization. The preparation method of the desulfurizing agent for fuel oil comprises the following steps: 1) mixing graphene oxide, a silicon source, alkali and a surfactant, reacting to obtain a reaction liquid A, and separating the reaction liquid A to obtain a reaction product A; 2) dispersing the reaction product A obtained in the step 1) in an organic solvent A, adding a silane coupling agent, reacting to obtain a reaction liquid B, and separating the reaction liquid B; 3) dispersing the reaction product B obtained in the step 2), a reducing agent and transition metal salt in deionized water, dropwise adding 0.2-0.6M sodium hydroxide solution at the feeding rate of 10-20ml/min, reacting, and separating to obtain the desulfurizing agent.)

1. The preparation method of the desulfurizer for the fuel oil is characterized by comprising the following steps:

1) mixing graphene oxide, a silicon source, alkali and a surfactant, reacting to obtain a reaction liquid A, and separating the reaction liquid A to obtain a reaction product A;

2) dispersing the reaction product A obtained in the step 1) in an organic solvent A, adding a silane coupling agent, reacting to obtain a reaction liquid B, and separating the reaction liquid B;

3) dispersing the reaction product B obtained in the step 2), a reducing agent and transition metal salt in deionized water, dropwise adding 0.2-0.6M sodium hydroxide solution at the feeding rate of 10-20ml/min, reacting, and separating to obtain the desulfurizing agent.

2. The preparation method according to claim 1, wherein in step 1), the graphene oxide, the silicon source, the alkali and the surfactant are dispersed in alcohol to obtain a mixed solution, the mixed solution is reacted in a hydrothermal kettle at 100-130 ℃ for 8-12 hours to obtain the reaction solution A, and the reaction solution A is washed, centrifuged and dried to obtain the reaction product A;

the graphene oxide, the silicon source, the alkali and the surfactant are mixed according to a mass ratio of 1: (10-30): (0.1-0.2): (2-10), wherein the mass concentration of the graphene oxide in the alcohol is 0.01 wt% -0.1 wt%.

3. The preparation method of claim 1, wherein in the step 2), the reaction product A obtained in the step 1) is dispersed in an organic solvent A, then a silane coupling agent is added, the reaction is carried out for not less than 6 hours at 20-90 ℃ to obtain the reaction liquid B, and the reaction liquid B is washed, centrifuged and dried to obtain the reaction product B;

wherein the mass ratio of the reaction product A to the silane coupling agent is 1: (8-12); the volume ratio of the silane coupling agent to the organic solvent A is 1 (5-8).

4. The preparation method according to claim 1, wherein in the step 3), the reaction product B obtained in the step 2), a reducing agent and a transition metal salt are dispersed in deionized water, 0.2-0.6M sodium hydroxide solution is dropwise added at a feeding rate of 15ml/min, the reaction is carried out at 80-120 ℃ for not less than 10h, and the desulfurizing agent is obtained after washing, separation and drying;

wherein the mass ratio of the reaction product B, the reducing agent and the transition metal salt obtained in the step 2) is 1: (0.5-2): (1-8), the concentration of the transition metal salt in the deionized water is 0.002-0.006g/mL, and the volume ratio of the deionized water to the sodium hydroxide solution is (11-13): 1.

5. The method according to any one of claims 1 to 4, wherein the silicon source is selected from one or more of tetraethyl orthosilicate, tetrabutyl orthosilicate, silica sol and sodium silicate; and/or

The alkali is at least one of sodium hydroxide, potassium hydroxide, concentrated ammonia water, sodium carbonate and urea; and/or

The surfactant is selected from one of quaternary ammonium salt surfactants; and/or

The silane coupling agent is selected from mercaptosilane coupling agents; and/or

The reducing agent is selected from at least one of sodium citrate, urea, chemical resistant acid and sodium borohydride; and/or

The transition metal salt is at least one selected from the group consisting of transition metal nitrate, transition metal chlorate and transition metal sulfate.

6. A desulfurizing agent for fuel oil, characterized in that it is obtained by the production method according to any one of claims 1 to 5.

7. The modified asphalt for the road base layer is characterized by comprising the following components in parts by mass: the modified asphalt is obtained by crosslinking reaction raw materials comprising 60-80 parts of petroleum asphalt, 5-30 parts of oil product desulfurization residue, 2-10 parts of monomer A, 1-5 parts of monomer B and 0.2-2 parts of initiator;

wherein the monomer A is at least one selected from double bond-terminated polyethylene glycol, and the molecular weight of the polyethylene glycol is 200-1000; the monomer B is selected from at least one of compounds shown in a formula I:

in the formula I, R₁、R₂、R₃、R₄Independently selected from H, C_1-5Alkyl and C_1-5One of alkyl carbonyl, x and y are independently selected from 1, 2, 3 or 4;

the oil product desulfurization residue is obtained by mixing a desulfurizing agent and sulfur-containing fuel oil, and then reacting and separating, wherein the desulfurizing agent is selected from the desulfurizing agent obtained by the preparation method of any one of claims 1 to 5 or the desulfurizing agent described in claim 6.

8. The modified asphalt of claim 4, wherein the monomer A is selected from polyethylene glycol dimethacrylate or polyethylene glycol diacrylate; and/or

The structural formula of the monomer B is shown as a formula II:

9. the modified asphalt of claim 4, wherein the initiator is selected from at least one of 2, 2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, propiophenone, and benzoin isobutyl ether.

10. A process for preparing the modified asphalt of any one of claims 7 to 9, wherein the petroleum asphalt, the oil desulfurization residue, the monomer a and the monomer B are added to an organic solvent B, then an initiator is added, and finally the modified asphalt is prepared by ultraviolet light radiation polymerization.

Technical Field

The application relates to a desulfurizer for fuel oil and a preparation method thereof, and application of oil product desulfurization residues in road base materials, belonging to the technical field of fuel oil desulfurization.

Background

With the rapid development of industry, the excessive use of a large amount of non-renewable resources such as coal, petroleum, natural gas and the like, the increasing scarcity of fossil energy, the popularization range of private cars is improved, and the demand for fuel oil is greatly increased. Sulfur-containing compounds in diesel oil are discharged into the atmosphere, become main air pollution sources, are main factors causing acid rain and haze formation, and have non-negligible influence on the aspects of human life. Therefore, the efficiency of the purification of the sulfur-containing substances is improved, and the sulfur content in the fuel oil must be controlled. The sulfur compounds which are difficult to remove are mainly inactive thiophene substances, such as benzothiophenes and thiothiophenes, which are sulfur compounds, belonging to aromatic heterocyclic systems, so that the key point of oil product desulfurization is the removal of thiophene sulfur compounds. There is therefore a need to develop more efficient and environmentally friendly desulfurization catalysts.

A large amount of byproducts are generated after the fuel oil is desulfurized, and at present, the sulfur-containing compound separated after the oil product is desulfurized is difficult to treat, so that the application field of finding the sulfur-containing compound is very important. The waterproof sealing layer is used as an important barrier for preventing rainfall and surface water from entering the roadbed body, and is one of key links for ensuring the long-term stability of the highway roadbed. For a waterproof closed structure of a highway, weather resistance, crack resistance and scouring resistance in an ultra-long service period need to be considered, so that the search for an asphalt cement with good performance is particularly important.

Disclosure of Invention

In order to solve the problems, the method provides a desulfurizer for fuel oil and a preparation method thereof, and application of oil product desulfurization residues in road base materials, and the method improves the adsorption effect on thiophene sulfur-containing compounds by adding graphene oxide and utilizing pi-pi interaction between the graphene oxide and the thiophene sulfur-containing compounds, thereby having higher desulfurization rate on the fuel oil; and the silicon dioxide can be simultaneously modified to be simultaneously sulfhydrylated with the graphene oxide, so that the specific surface area of the desulfurizer is increased, the contact area of the desulfurizer and sulfide is greatly increased, more anchor points are provided for the load of the metal catalyst, and the sulfur removal rate is further improved. And the oil product desulfurization residue obtained after the fuel oil is treated by the desulfurizer is crosslinked with asphalt and other monomers, so that the strength of the modified asphalt is greatly improved, the cracking resistance and the aging resistance of the modified asphalt are improved, and the modified asphalt has good performance as a road base material.

According to an aspect of the present application, there is provided a method for preparing a desulfurizing agent for fuel oil, comprising the steps of:

1) mixing graphene oxide, a silicon source, alkali and a surfactant, reacting to obtain a reaction liquid A, and separating the reaction liquid A to obtain a reaction product A; in the process, silicon dioxide can be loaded on graphene oxide, and the silicon dioxide can be modified to graft hydroxyl on the surface of the silicon dioxide;

2) dispersing the reaction product A obtained in the step 1) in an organic solvent A, adding a silane coupling agent, reacting to obtain a reaction liquid B, and separating the reaction liquid B; by adding the silane coupling agent, the groups on the surfaces of the graphene oxide and the silicon dioxide are substituted, so that the specific surface area of the prepared desulfurizer is greatly increased, and the desulfurization efficiency is improved.

3) Dispersing the reaction product B obtained in the step 2), a reducing agent and transition metal salt in deionized water, dropwise adding 0.2-0.6M sodium hydroxide solution at the feeding rate of 10-20ml/min, reacting, and separating to obtain the desulfurizing agent. In the step, transition metal oxide is loaded on the surface of the modified graphene oxide loaded silicon dioxide, so that the desulfurization rate is further improved; by controlling the feeding speed of the sodium hydroxide solution, the particle size of the transition metal compound is more uniform, and the dispersion on the graphene oxide is better.

Optionally, in step 1), dispersing the graphene oxide, a silicon source, an alkali and a surfactant in alcohol to obtain a mixed solution, reacting in a hydrothermal kettle at 100-130 ℃ for 8-12 hours to obtain a reaction solution a, and washing, centrifuging and drying the reaction solution a to obtain a reaction product a;

the graphene oxide, the silicon source, the alkali and the surfactant are mixed according to a mass ratio of 1: (10-30): (0.1-0.2): (2-10), wherein the mass concentration of the graphene oxide in the alcohol is 0.01 wt% -0.1 wt%.

Preferably, the mass ratio of the graphene oxide to the silicon source to the alkali to the surfactant is 1: (15-25): (0.13-0.17): (5-7); more preferably 1:20:0.15: 6.

Preferably, the mass concentration of the graphene oxide in the alcohol is 0.05 wt%.

Optionally, the alcohol is ethanol.

Optionally, in the step 2), dispersing the reaction product A obtained in the step 1) in an organic solvent A, adding a silane coupling agent, reacting at 20-90 ℃ for not less than 6 hours to obtain a reaction solution B, and washing, centrifuging and drying the reaction solution B to obtain a reaction product B;

wherein the mass ratio of the reaction product A to the silane coupling agent is 1: (8-12); the volume ratio of the silane coupling agent to the organic solvent A is 1 (5-8).

Optionally, the organic solvent a is at least one of methanol, ethanol, acetone, dichloromethane and chloroform, preferably ethanol.

Preferably, the mass ratio of the reaction product A to the silane coupling agent is 1: 10; the volume ratio of the silane coupling agent to the organic solvent A is 1: 7.

Optionally, in the step 3), dispersing the reaction product B obtained in the step 2), a reducing agent and a transition metal salt in deionized water, dropwise adding 0.2-0.6M sodium hydroxide solution at a feeding rate of 15ml/min, reacting at 80-120 ℃ for at least 10h, washing, separating and drying to obtain the desulfurizing agent; preferably, 0.4M sodium hydroxide solution is dropwise added at the feeding rate of 15ml/min, and the reaction is carried out for 12 hours at the temperature of 100 ℃;

wherein the mass ratio of the reaction product B, the reducing agent and the transition metal salt obtained in the step 2) is 1: (0.5-2): (1-8), the concentration of the transition metal salt in the deionized water is 0.002-0.006g/mL, and the volume ratio of the deionized water to the sodium hydroxide solution is (11-13): 1.

Preferably, the mass ratio of the reaction product B, the reducing agent and the transition metal salt obtained in the step 2) is 1: (1-1.5): (3-6), more preferably 1:1.2: 4; the concentration of the transition metal salt in the deionized water is 0.004g/mL, and the volume ratio of the deionized water to the sodium hydroxide solution is 12: 1.

Optionally, the silicon source is selected from one or more of tetraethyl orthosilicate, tetrabutyl orthosilicate, silica sol and sodium silicate, preferably tetraethyl orthosilicate; and/or

The alkali is at least one of sodium hydroxide, potassium hydroxide, concentrated ammonia water, sodium carbonate and urea; preferably sodium hydroxide; and/or

The surfactant is selected from one of quaternary ammonium salt surfactants; preferably dodecyl dimethyl benzyl ammonium chloride; and/or

The silane coupling agent is selected from mercaptosilane coupling agents; preferably at least one of mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptopropylmethyldimethoxysilane, 2-mercaptoethyltriethoxysilane, and mercaptopropylmethyldiethoxysilane; more preferably mercaptopropyltrimethoxysilane; and/or

The reducing agent is selected from at least one of sodium citrate, urea, chemical resistant acid and sodium borohydride; preferably sodium citrate; and/or

The transition metal salt is at least one selected from transition metal nitrate, transition metal chlorate and transition metal sulfate, preferably cobalt salt, manganese salt, molybdenum salt and nickel salt, and more preferably cobalt nitrate hexahydrate.

According to another aspect of the present application, there is provided a desulfurizing agent for fuel oil, which is obtained by the preparation method of any one of the above.

According to still another aspect of the present application, there is provided a modified asphalt for a road base layer, comprising, in parts by mass: the modified asphalt is obtained by crosslinking reaction raw materials comprising 60-80 parts of petroleum asphalt, 5-30 parts of oil product desulfurization residue, 2-10 parts of monomer A, 1-5 parts of monomer B and 0.2-2 parts of initiator;

wherein the monomer A is at least one selected from double bond-terminated polyethylene glycol, the molecular weight of the polyethylene glycol is 200-1000, and the monomer B is at least one selected from compounds shown in formula I:

in the formula I, R₁、R₂、R₃、R₄Independently selected from H, C_1-5Alkyl and C_1-5One of alkyl carbonyl, x and y are independently selected from 1, 2, 3 or 4;

the oil product desulfurization residue is obtained by mixing a desulfurizing agent and sulfur-containing fuel oil, and then reacting and separating, wherein the desulfurizing agent is selected from the desulfurizing agent obtained by any one of the preparation methods or the desulfurizing agent.

Preferably, the modified asphalt is obtained by crosslinking reaction raw materials comprising 65-75 parts of petroleum asphalt, 10-20 parts of oil product desulfurization residue, 5-7 parts of monomer A, 2-4 parts of monomer B and 0.5-1 part of initiator;

r in the monomer B₁Is selected from C_1-4One of the alkylcarbonyl groups, R₂Is selected from C_1-4One of the alkyl radicals, R₃Is selected from C_1-4One of the alkylcarbonyl groups, R₄Is selected from C_1-4One of the alkyl groups.

More preferably, the modified asphalt is obtained by crosslinking reaction raw materials comprising 70 parts of petroleum asphalt, 15 parts of oil product desulfurization residue, 6 parts of monomer A, 3 parts of monomer B and 0.7 part of initiator.

Optionally, the monomer A is selected from polyethylene glycol dimethacrylate or polyethylene glycol diacrylate, preferably polyethylene glycol dimethacrylate; and/or

The structural formula of the monomer B is shown as a formula II:

optionally, the initiator is selected from at least one of 2, 2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, propiophenone and benzoin isobutyl ether, preferably 2, 2-dimethoxy-2-phenylacetophenone.

According to yet another aspect of the present application, there is provided a process for preparing the modified asphalt of any of the above, the process comprising: and adding the petroleum asphalt, the oil product desulfurization residue, the monomer A and the monomer B into an organic solvent B, then adding an initiator, and finally carrying out ultraviolet radiation polymerization to obtain the modified asphalt.

Optionally, the wavelength of the ultraviolet light is 350-380nm, and the irradiation time is 20-50 min.

Optionally, the organic solvent B is selected from at least one of dichloromethane, chloroform, tetrahydrofuran, ethyl acetate, toluene and chlorobenzene, preferably ethyl acetate.

Alternatively, the concentration of monomer A in the organic solvent B is 0.01-0.1g/mL, preferably 0.05 g/mL.

Benefits of the present application include, but are not limited to:

1. according to the preparation method of the desulfurizer for the fuel oil, the graphene oxide is added, and the adsorption effect on the thiophene sulfur-containing compound is improved by utilizing the pi-pi interaction between the graphene oxide and the thiophene sulfur-containing compound, so that the desulfurizer for the fuel oil has higher sulfur removal rate; and the silicon dioxide can be simultaneously modified to be simultaneously sulfhydrylated with the graphene oxide, so that the specific surface area of the desulfurizer is increased, the contact area of the desulfurizer and sulfide is greatly increased, more anchor points are provided for the load of the metal catalyst, and the sulfur removal rate is further improved.

2. According to the sulfur remover, the graphene oxide contains a large number of functional groups, the silicon dioxide is hydroxylated, and then the mercapto silane coupling agent is added to replace the groups on the surfaces of the graphene oxide and the silicon dioxide, so that the sulfur remover can be used as an oil desulfurization residue to modify asphalt after being used for desulfurization of fuel oil, and can be used as a road base material, thereby being beneficial to recycling of the oil desulfurization residue.

3. According to the modified asphalt, because the oil product desulfurization residue contains the desulfurizing agent, the coupling of the graphene oxide and the mercaptosilane grafted on the silicon dioxide in the desulfurizing agent can not only perform a crosslinking reaction with the monomer A and the monomer B, but also perform a grafting crosslinking reaction with an active group in the asphalt, and the graphene oxide is taken as a crosslinking point to firmly combine various molecular chains together through the molecular chains, so that the strength of the modified asphalt is greatly improved, the cracking resistance and the aging resistance of the modified asphalt are improved, and the modified asphalt has better stability; in addition, a large amount of sulfur-containing compounds and rich groups exist in the oil product desulfurization residue, and the sulfur-containing compounds and the rich groups can also perform cross-linking reaction with the groups grafted on the graphene oxide and the silicon dioxide, the monomer A, the monomer B and the asphalt, so that the petroleum asphalt is modified, and the performance of the petroleum asphalt is improved.

Detailed Description

The present application will be described in detail with reference to examples, but the present application is not limited to these examples.

Unless otherwise specified, the raw materials and catalysts in the examples of the present application were all purchased commercially.

Example 1 preparation of desulfurizing agent and Performance test

The preparation method of the desulfurizing agent 1# comprises the following steps:

1) dispersing 20g of graphene oxide dispersion liquid (hereinafter referred to as GO dispersion liquid) with the mass concentration of 5 wt%, 20g of tetraethyl orthosilicate, 0.15g of sodium hydroxide and 6g of dodecyl dimethyl benzyl ammonium chloride in 2000g of ethanol, reacting for 10 hours in a hydrothermal kettle at 120 ℃ to obtain reaction liquid A, and washing, centrifuging and drying the reaction liquid A to obtain a reaction product A, namely graphene-loaded silicon dioxide;

2) dispersing the graphene-loaded silicon dioxide obtained in the step 1) in ethanol, adding mercaptopropyl trimethoxysilane, reacting for 8 hours at 50 ℃ to obtain reaction liquid B, washing, centrifuging and drying the reaction liquid B to obtain a reaction product B, namely modified graphene-loaded silicon dioxide; wherein the mass ratio of the reaction product A to mercaptopropyl trimethoxysilane is 1:10, and the volume ratio of the mercaptopropyl trimethoxysilane to ethanol is 1: 6;

3) dispersing the reaction product B obtained in the step 2), sodium citrate and cobalt nitrate hexahydrate in deionized water, dropwise adding 0.4M sodium hydroxide solution at the feeding rate of 15mL/min, carrying out reflux reaction at 100 ℃ for 12h, washing, separating and drying to obtain a desulfurizer 1#, wherein the mass ratio of the reaction product B, the sodium citrate and the cobalt nitrate hexahydrate is 1:1.2:4, the concentration of the cobalt nitrate hexahydrate in the deionized water is 0.004g/mL, and the volume ratio of the deionized water to the sodium hydroxide solution is 12: 1.

According to the preparation steps of the desulfurizer 1#, the preparation conditions of the desulfurizer 2# -5#, the desulfurizer D1# -D4#, the desulfurizer 2# -5#, and the desulfurizer D1# -D4# are shown in Table 1, and the rest conditions are the same as the desulfurizer 1 #.

In addition, 5g of desulfurizer No. 1-5, desulfurizer D1-D4 and 500g of fuel oil (sulfur content is 5.2%) are respectively mixed and added into a reaction kettle to react at the reaction temperature of 400 ℃ and under the pressure of 8MPa, reaction products are centrifugally separated, upper layer desulfurized oil product No. 1-5 and D1-D4 are respectively sent to be subjected to sulfur element analysis, and the results are shown in Table 1, and lower layer precipitates are oil product desulfurized residues No. 1-5 and D1-D4.

TABLE 1

Example 2 preparation and Performance testing of modified asphalt

Respectively taking 150g of oil product desulfurization residue No. 1-5 and No. D1-D4, adding 700g of petroleum asphalt, 60g of polyethylene glycol dimethacrylate (molecular weight is 400) and 30g of monomer B into 1200mL of ethyl acetate, uniformly mixing, then adding 7g of 2, 2-dimethoxy-2-phenyl acetophenone, and respectively obtaining modified asphalt No. 1-5 and No. D1-D4 by ultraviolet irradiation with the wavelength of 350nm for 30min, wherein the structural formula of the monomer B is as follows:

in addition, modified asphalts 1a #, 1b #, 1c #, and 1d # were prepared, respectively. The modified asphalt 1a # is different from the modified asphalt 1# in that a monomer B of the modified asphalt 1a # is dimercaptothioethyl ether, and the rest conditions are the same; the modified asphalt 1b # is different from the modified asphalt 1# in that the monomer A is not added into the modified asphalt 1b # and the rest conditions are the same; the modified asphalt 1c # is different from the modified asphalt 1# in that the oil product desulfurization residue 1# is not added to the modified asphalt 1c # and the rest conditions are the same; the modified asphalt 1d # is different from the modified asphalt 1# in that the modified asphalt 1d # uses a desulfurizing agent 1# to replace the oil product desulfurization residue 1#, and the rest conditions are the same.

According to road engineering asphalt and asphalt mixture experimental regulation JTG E20-2011, modified asphalt 1# -5#, 1a # -1D # and D1# -D4# are tested, and the results are shown in Table 2.

TABLE 2

As can be seen from tables 1 and 2, the desulfurizer of the invention has high desulfurization rate for fuel oil, and the obtained oil desulfurization residue can modify asphalt, and the obtained modified asphalt has high low-temperature crack resistance, higher aging resistance and elastic adjustment capability; from the isolated softening point data, the modified asphalt of the invention has higher stability.

The above description is only an example of the present application, and the protection scope of the present application is not limited by these specific examples, but is defined by the claims of the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical idea and principle of the present application should be included in the protection scope of the present application.