Hydrogenation catalyst as well as preparation method and application thereof
By using nickel particle catalysts supported by oxygen-deficient carriers, the problem of low saturation efficiency of aromatic hydrogenation is solved, and efficient catalysis of aromatics and cycloolefins is achieved with excellent hydrogenation effect.
Patent Information
- Application Number
- CN202510811025.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-17
- Publication Date
- 2025-09-30
AI Technical Summary
Existing technologies have difficulty in efficiently catalyzing the hydrogenation saturation of aromatics, leading to environmental pollution and problems with the thermal oxidation stability of jet fuel.
A hydrogenation catalyst using TiO2-x1, WO3-x2, CeO2-x3 and Fe2O3-x4 as carriers is loaded with nickel particles, and nickel nucleation growth is optimized through oxygen defects. The preparation method includes the steps of mixing ammonium citrate solution and nickel salt solution, dispersing, and roasting to form an active material.
It achieves efficient hydrogenation saturation of aromatics and cycloolefins, improves the thermal oxidation stability of jet fuel, reduces nickel particle size, and improves catalytic activity.
Smart Images
Figure BDA0005453961150000081 
Figure BDA0005453961150000091
Abstract
Description
Technical Field
[0001] The present application relates to the field of catalytic technology, and in particular to a hydrogenation catalyst and a preparation method and application thereof. Background Art
[0002] Hydrogenation is a widely used reaction in the chemical industry, with the saturation hydrogenation of aromatic hydrocarbons being the most widely used. Aromatic hydrocarbons are significant pollutants harmful to the ecological environment, but they are also important raw materials for high-value-added products. Their direct emissions and incomplete combustion can cause environmental pollution. Hydrogenation of aromatic hydrocarbons is an attractive approach to addressing these issues. Hydrogenation of fuels containing large amounts of unsaturated hydrocarbons can remove harmful components or change the hydrocarbon composition, radically improving the thermal oxidation stability of jet fuels, even under harsh conditions (where additives are generally ineffective at high temperatures). In fact, hydrogenation is more likely to alter the hydrocarbon composition of jet fuels, such as the aromatic content, thereby promoting or retarding oxidation and / or deposition. Summary of the Invention
[0003] In view of this, the embodiments of the present application provide a hydrogenation catalyst, a preparation method and an application thereof.
[0004] In a first aspect, the present application provides a hydrogenation catalyst, comprising:
[0005] A carrier comprising TiO 2-x1 , WO 3-x2 、CeO 2-x3 and Fe2O 3-x4 At least one of;
[0006] An active material, the active material being located on the surface of the carrier, and the active material comprising nickel;
[0007] Among them, x1 is greater than 0 and less than 2; x2 is greater than 0 and less than 3; x3 is greater than 0 and less than 2; x4 is greater than 0 and less than 3.
[0008] In one embodiment, the active material comprises nickel particles;
[0009] Preferably, the particle size of the nickel particles is greater than or equal to 1 nm and less than or equal to 3 nm;
[0010] Preferably, the support TiO 2-x1 In the equation, the ratio of x1 to 2 is greater than 0 and less than or equal to 10%;
[0011] Preferably, the carrier WO 3-x2 In the equation, the ratio of x2 to 3 is greater than 0 and less than or equal to 10%;
[0012] Preferably, the CeO2-x3 In the equation, the ratio of x3 to 2 is greater than 0 and less than or equal to 10%;
[0013] Preferably, the carrier Fe2O 3-x4 , the ratio of x4 to 3 is greater than 0 and less than or equal to 10%.
[0014] In one embodiment, the active material content is 1 to 40 wt % based on the total mass of the hydrogenation catalyst.
[0015] A second aspect of the present application provides a method for preparing the aforementioned hydrogenation catalyst, comprising:
[0016] mixing the ammonium citrate solution and the nickel salt solution to obtain a metal organic complex solution;
[0017] dispersing the carrier in a first solvent to obtain a first dispersion;
[0018] mixing the first dispersion and the metal organic complex solution, and reacting to obtain a precursor;
[0019] The precursor is calcined in a reducing atmosphere to obtain the hydrogenation catalyst.
[0020] In one embodiment, the molar ratio of ammonium citrate in the ammonium citrate solution to the nickel salt in the nickel salt solution is greater than 0 and less than or equal to 3;
[0021] Preferably, the molar ratio of ammonium citrate in the ammonium citrate solution to the nickel salt in the nickel salt solution is greater than or equal to 1.5 and less than or equal to 2.5;
[0022] Preferably, the first solvent comprises water and / or alcohol.
[0023] In one embodiment, the reducing atmosphere comprises hydrogen;
[0024] Preferably, the calcination temperature is 400-600°C and the calcination time is 2-4 hours;
[0025] Preferably, the step of dispersing the carrier in the first solvent comprises: dispersing the carrier in the first solvent under ultrasonic conditions.
[0026] In a third aspect, the present application provides a use of the aforementioned hydrogenation catalyst in hydrogenation, wherein the hydrogenation catalyst is used to hydrogenate unsaturated molecules;
[0027] Preferably, the unsaturated molecules include at least one of olefins, cycloolefins, aromatic hydrocarbons and condensed ring aromatic hydrocarbons;
[0028] Preferably, the unsaturated molecule includes at least one of 1-hexene, toluene, quinoline, quinoline derivatives, naphthalene, naphthalene derivatives, fluorene, fluorene derivatives, dicyclopentadiene, dicyclopentadiene derivatives, norbornene, and norbornene derivatives.
[0029] According to the hydrogenation catalyst provided in the examples of the present application, an active material comprising nickel is dispersed on the surface of a support, resulting in excellent hydrogenation activity. The support has oxygen vacancies, which reduce the size of the supported nickel particles and their average coordination number, thereby optimizing substrate adsorption and / or desorption, thereby catalyzing the hydrogenation saturation of aromatic hydrocarbons and cycloolefins. DETAILED DESCRIPTION
[0030] The following is a clear and complete description of the technical solutions in the embodiments of this application. Obviously, the embodiments described are only part of the embodiments of this application, not all of them. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.
[0031] In addition, in order to better illustrate the present application, numerous specific details are provided in the following detailed description. Those skilled in the art will understand that the present application can be practiced without certain specific details. In some examples, methods and means well known to those skilled in the art are not described in detail in order to highlight the main purpose of the present application.
[0032] In addition, the terms "first", "second", etc., if used, are merely used to distinguish and describe, and should not be understood as indicating or implying relative importance.
[0033] The first aspect of the present application provides a hydrogenation catalyst, comprising: a carrier and an active material, wherein the active material is located on the surface of the carrier, and the carrier comprises TiO 2-x1 , WO 3-x2 、CeO 2-x3 and Fe2O 3-x4At least one of the following: the active material includes nickel; wherein x1 is greater than 0 and less than 2 (for example, it can be 0.1, 0.2, 0.4, 0.6, 0.8, 1, 1.2, 1.4, 1.6, 1.8, etc.); x2 is greater than 0 and less than 3 (for example, it can be 0.1, 0.2, 0.4, 0.6, 0.8, 1, 1.2, 1.4, 1.6, 1.8, 2, 2.2, 2.4, 2 .6 or 2.8, etc.); x3 is greater than 0 and less than 2 (for example, it can be 0.1, 0.2, 0.4, 0.6, 0.8, 1, 1.2, 1.4, 1.6, 1.8, etc.); x4 is greater than 0 and less than 3 (for example, it can be 0.1, 0.2, 0.4, 0.6, 0.8, 1, 1.2, 1.4, 1.6, 1.8, 2, 2.2, 2.4, 2.6 or 2.8, etc.).
[0034] According to the hydrogenation catalyst provided in the embodiment of the present application, the active material comprising nickel is dispersed on the surface of the carrier, so that the hydrogenation activity of the hydrogenation catalyst is excellent. Among them, there is an oxygen defect in the carrier, and the oxygen defect can reduce the size of the loaded nickel particles, reduce its average coordination number, thereby optimizing the adsorption and / or desorption of the substrate, thereby catalyzing the hydrogenation saturation of aromatic hydrocarbons and polycyclic olefins. Exemplarily, the carrier with oxygen defects can provide more attachment sites for nickel nucleation growth, and oxygen defects will produce an electron-rich effect, which can accelerate the low-temperature reduction of nickel and reduce the size of nickel nucleation.
[0035] Optionally, the active material includes nickel particles, and the particle size of the nickel particles is 1 to 3 nm, for example, 1 nm, 2 nm, or 3 nm, etc. The nickel particles have a small particle size, which facilitates uniform distribution on the surface of the carrier.
[0036] In one embodiment, the carrier has oxygen defects therein.
[0037] Optionally, on a TiO support 2-x1 In the above ratio range, the ratio of x1 to 2 is greater than 0 and less than or equal to 10%, for example, it can be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc. Compared with the above ratio range, it is impossible to prepare TiO with a ratio of x1 to 2 greater than 10%. 2-x1 .
[0038] Optionally, in the carrier WO 3-x2 In the above ratio range, the ratio of x2 to 3 is greater than 0 and less than or equal to 10%, for example, it can be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc. Compared with the above ratio range, it is impossible to prepare WO with a ratio of x2 to 3 greater than 10%. 3-x2 .
[0039] Optionally, CeO 2-x3In the above ratio range, the ratio of x3 to 2 is greater than 0 and less than or equal to 10%, for example, it can be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc. Compared with the above ratio range, it is impossible to prepare CeO with a ratio of x3 to 2 greater than 10%. 2-x3 .
[0040] Optionally, on a carrier Fe2O 3-x4 In the above ratio range, the ratio of x4 to 3 is greater than 0 and less than or equal to 10%, for example, it can be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc. Compared with the above ratio range, it is impossible to prepare Fe2O with a ratio of x4 to 3 greater than 10%. 3-x4 . In one embodiment, based on the total mass of the hydrogenation catalyst, the content of the active material is 1 to 40 wt%, for example, it can be 1 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt% or 40 wt%, etc. As a result, the catalytic hydrogenation effect of the hydrogenation catalyst is excellent. Relative to the content of the above-mentioned active material, when the content of the active material is lower than 1 wt%, the catalytic hydrogenation effect of the hydrogenation catalyst is not good; when the content of the active material is higher than 40 wt%, the active material will agglomerate, resulting in a decrease in the hydrogenation effect of the hydrogenation catalyst.
[0041] The second aspect of the present application provides a method for preparing the aforementioned hydrogenation catalyst, comprising the following steps.
[0042] S100: In order to uniformly disperse the nickel precursor, the ammonium citrate solution and the nickel salt solution are mixed to obtain a metal organic complex solution.
[0043] In one embodiment, the molar ratio of ammonium citrate in the ammonium citrate solution to nickel salt in the nickel salt solution is greater than 0 and less than or equal to 3, for example, 0.5, 1, 1.5, 2, 2.5, or 3. This facilitates the full reaction of nickel salt and ammonium citrate to form a metal organic complex.
[0044] In a preferred embodiment, the molar ratio of the ammonium citrate in the ammonium citrate solution to the nickel salt in the nickel salt solution is greater than or equal to 1.5 and less than or equal to 2.5, so that the nickel salt reacts more fully with the ammonium citrate.
[0045] For example, ammonium citrate can be used to adjust the particle size of nickel particles so that the particle size of the nickel particles is 1 to 3 nm.
[0046] S200: dispersing the carrier in a first solvent to obtain a first dispersion.
[0047] Optionally, the first solvent comprises water and / or alcohol.
[0048] Optionally, the step of dispersing the carrier in the first solvent includes dispersing the carrier in the first solvent under ultrasonic conditions. Thus, the carrier is dispersed more evenly, which is conducive to obtaining a hydrogenation catalyst with excellent performance.
[0049] S300: mixing the first dispersion and the metal organic complex solution, slowly anchoring the metal organic complex on the surface of the carrier, and obtaining a precursor after sufficient reaction.
[0050] For example, the support has oxygen defects, which can provide more attachment sites for nickel nucleation and growth, thereby facilitating the acquisition of a hydrogenation catalyst with a higher nickel loading.
[0051] S400: calcining the precursor in a reducing atmosphere to remove the ammonium citrate complex and reduce nickel to obtain the hydrogenation catalyst.
[0052] In one embodiment, the reducing atmosphere includes hydrogen. For example, oxygen defects in the support can produce an electron-rich effect, which can accelerate the low-temperature reduction of nickel, reduce the size of nickel nuclei, and make the nickel particles in the hydrogenation catalyst smaller.
[0053] In one embodiment, the calcination temperature is 400-600° C. (eg, 400° C., 500° C., or 600° C.), and the calcination time is 2-4 h (eg, 2 h, 3 h, or 4 h).
[0054] In a third aspect, the present application provides a use of the aforementioned hydrogenation catalyst in hydrogenation.
[0055] Optionally, unsaturated organic molecules are hydrogenated using the hydrogenation catalyst.
[0056] Optionally, the unsaturated organic molecules include at least one of aromatic hydrocarbons and polycyclic olefins that are hydrogenated.
[0057] For example, the hydrogenation catalyst hydrogenates aromatic hydrocarbons to obtain saturated cycloalkanes; for example, the hydrogenation catalyst hydrogenates polycyclic olefins to obtain saturated polycyclic alkanes.
[0058] Optionally, the unsaturated molecules include at least one of chain alkenes, cycloalkenes, aromatic hydrocarbons and condensed ring aromatic hydrocarbons.
[0059] Optionally, the unsaturated molecule includes at least one of 1-hexene, toluene, quinoline, quinoline derivatives, naphthalene, naphthalene derivatives, fluorene, fluorene derivatives, dicyclopentadiene, dicyclopentadiene derivatives, norbornene and norbornene derivatives.
[0060] The present application is further described below in conjunction with specific examples. It should be noted that the following examples are only used to explain the present application and are not to be construed as limiting the present application.
[0061] Example 1
[0062] The preparation method of the hydrogenation catalyst comprises the following steps:
[0063] 1. Place 1g TiO2 in a tube furnace and calcine it at 500℃ for 2h under hydrogen atmosphere to obtain TiO2 with oxygen defects. 2-x1 Vector, the ratio of x1 to 2 is 6%.
[0064] 2. Dissolve 1.5mmol of ammonium citrate in 20mL of water, then add 20mL of 1mmol of Ni 2+ The aqueous solution of 2,4-dimethyl-1-thiazolyl-1-ol was added to the mixed solution and stirred at room temperature for 8 h to obtain an aqueous solution of nickel citrate complex.
[0065] 3. Add 0.5g of TiO with oxygen defects 2-x The support was uniformly dispersed in 50 mL of water and ultrasonically dispersed for 1 h. Subsequently, 5 mL of the above-mentioned ammonium citrate complex aqueous solution was added, stirred for 12 h, further centrifuged and dried, and calcined at 500° C. for 2 h under a hydrogen atmosphere to obtain a hydrogenation catalyst.
[0066] ICP (inductively coupled plasma) characterization results show that the Ni content in the hydrogenation catalyst of this embodiment is 2.5%.
[0067] Example 2
[0068] The preparation method of the hydrogenation catalyst is basically the same as that of Example 1, except that the metal precursor used is a 1 mmol Ni 2+ of aqueous solution.
[0069] ICP (inductively coupled plasma) characterization results show that the Ni content in the hydrogenation catalyst of this embodiment is 2.5%.
[0070] Example 3
[0071] The preparation method of hydrogenation catalyst is basically the same as that in Example 1, except that in step 2, 20 mL of 4 mmol Ni 2+ The aqueous solution was added to the mixed solution.
[0072] ICP (inductively coupled plasma) characterization results show that the Ni content in the hydrogenation catalyst of this embodiment is 9.8%.
[0073] Example 4
[0074] The preparation method of hydrogenation catalyst is basically the same as that in Example 1, except that in step 2, 20 mL of 8 mmol Ni 2+ The aqueous solution was added to the mixed solution.
[0075] ICP (inductively coupled plasma) characterization results show that the Ni content in the hydrogenation catalyst of this embodiment is 18.1%.
[0076] Example 5
[0077] The preparation method of hydrogenation catalyst is basically the same as that in Example 1, except that in step 2, 20 mL of 16 mmol Ni 2+ The aqueous solution was added to the mixed solution.
[0078] ICP (inductively coupled plasma) characterization results show that the Ni content in the hydrogenation catalyst of this embodiment is 28.8%.
[0079] Example 6
[0080] The preparation method of hydrogenation catalyst is basically the same as that in Example 1, except that in step 2, 20 mL of 32 mmol Ni 2+ The aqueous solution was added to the mixed solution.
[0081] ICP (inductively coupled plasma) characterization results show that the Ni content in the hydrogenation catalyst of this embodiment is 38.9%.
[0082] Example 7
[0083] The preparation method of the hydrogenation catalyst is basically the same as that in Example 1, except that the carrier used is WO with oxygen defects. 3-x2 , the ratio of x2 to 3 is 6%.
[0084] ICP (inductively coupled plasma) characterization results show that the Ni content in the hydrogenation catalyst of this embodiment is 2.4%.
[0085] Example 8
[0086] The preparation method of the hydrogenation catalyst is basically the same as that in Example 1, except that the carrier used is CeO with oxygen defects. 2-x3 , the ratio of x3 to 2 is 6%.
[0087] ICP (inductively coupled plasma) characterization results show that the Ni content in the hydrogenation catalyst of this embodiment is 2.5%.
[0088] Example 9
[0089] The preparation method of the hydrogenation catalyst is basically the same as that of Example 1, except that the carrier used is Fe2O3 with oxygen defects. 3-x4 , the ratio of x4 to 3 is 6%.
[0090] ICP (inductively coupled plasma) characterization results show that the Ni content in the hydrogenation catalyst of this embodiment is 2.3%.
[0091] Example 10
[0092] The preparation method of the hydrogenation catalyst is basically the same as that in Example 1, except that the carrier used is TiO 2-x1 Vector, the ratio of x1 to 2 is 3%.
[0093] Example 11
[0094] The preparation method of the hydrogenation catalyst is basically the same as that in Example 1, except that the carrier used is TiO 2-x1 Vector, the ratio of x1 to 2 is 10%.
[0095] Example 12
[0096] The preparation method of the hydrogenation catalyst is basically the same as that of Example 1, except that ammonium citrate is not added in step 2.
[0097] Example 13
[0098] The preparation method of the hydrogenation catalyst is basically the same as that of Example 1, except that 1 mmol of ammonium citrate is dissolved in 20 mL of water, and then 20 mL of 1 mmol of Ni 2+ The aqueous solution was added to the above mixed solution.
[0099] Example 14
[0100] The preparation method of the hydrogenation catalyst is basically the same as that of Example 1, except that 2.5 mmol of ammonium citrate is dissolved in 20 mL of water, and then 20 mL of 1 mmol of Ni 2+ The aqueous solution was added to the above mixed solution.
[0101] Example 15
[0102] The preparation method of the hydrogenation catalyst is basically the same as that of Example 1, except that 4 mmol of ammonium citrate is dissolved in 20 mL of water, and then 20 mL of 1 mmol of Ni 2+ The aqueous solution was added to the above mixed solution.
[0103] Comparative Example 1
[0104] The preparation method of the hydrogenation catalyst is basically the same as that of Example 1, except that the carrier used is TiO2 that has not been treated in step 1.
[0105] ICP (inductively coupled plasma) characterization results show that the Ni content in the hydrogenation catalyst of this embodiment is 2.5%.
[0106] The substrates (including toluene, quinoline, naphthalene, fluorene, dicyclopentadiene, and norbornene) were hydrogenated using the hydrogenation catalysts of Examples 1 to 15 and Comparative Example 1. The obtained products, their conversion rates, and their selectivities are shown in Table 1.
[0107] Table 1
[0108]
[0109]
[0110] The hydrogenation conditions include: 5 mmol of reaction substrate, 50 bar of reaction pressure, 100 mg of hydrogenation catalyst, 4 hours of reaction time (3 hours for Example 4, 2 hours for Example 5, 1 hour for Example 6, 0.5 hours for Example 7, and 2 hours for Example 12), and a reaction temperature of 120°C (when the reactant is toluene), 60°C (when the reactants are 1-hexene, dicyclopentadiene, or norbornene), or 180°C (when the reactants are quinoline, naphthalene, or fluorene).
[0111] It should be noted that the "Hydrogenation Catalyst Used" column in Table 1 indicates that the hydrogenation catalyst used is the hydrogenation catalyst of a specific example or comparative example. For purposes of illustration, the first row indicates that the hydrogenation catalyst used is the hydrogenation catalyst of Example 1, the substrate is toluene, and the product obtained from the catalytic reaction of toluene using the hydrogenation catalyst of Example 1 is methylcyclohexane with a yield of 100%. The meanings of the remaining rows refer to the first row and are not further elaborated here.
[0112] The basic principles of the present application have been described above in conjunction with specific embodiments. However, it should be noted that the advantages, strengths, and effects mentioned in this application are merely illustrative and not restrictive, and it should not be assumed that these advantages, strengths, and effects are required of each embodiment of this application. In addition, the specific details disclosed above are merely illustrative and facilitating understanding, and are not restrictive. The above details do not limit this application to necessarily being implemented using the above specific details.
[0113] The above description has been provided for the purpose of illustration and description. In addition, this description is not intended to limit the embodiments of the present application to the forms disclosed herein. Although a number of example aspects and embodiments have been discussed above, those skilled in the art will recognize certain variations, modifications, alterations, additions, and sub-combinations thereof.
Claims
1. A hydrogenation catalyst, characterized in that include: A carrier comprising TiO 2-x1 , WO 3-x2 、CeO 2-x3 and Fe2O 3-x4 At least one of; An active material, the active material being located on the surface of the carrier, and the active material comprising nickel; Among them, x1 is greater than 0 and less than 2; x2 is greater than 0 and less than 3; x3 is greater than 0 and less than 2; x4 is greater than 0 and less than 3.
2. The hydrogenation catalyst according to claim 1, characterized in that The active material includes nickel particles; Preferably, the particle size of the nickel particles is greater than or equal to 1 nm and less than or equal to 3 nm.
3. The hydrogenation catalyst according to claim 1, characterized in that On the support TiO 2-x1 In the equation, the ratio of x1 to 2 is greater than 0 and less than or equal to 10%; Preferably, the carrier WO 3-x2 In the equation, the ratio of x2 to 3 is greater than 0 and less than or equal to 10%; Preferably, the CeO 2-x3 In the equation, the ratio of x3 to 2 is greater than 0 and less than or equal to 10%; Preferably, the carrier Fe2O 3-x4 , the ratio of x4 to 3 is greater than 0 and less than or equal to 10%.
4. The hydrogenation catalyst according to claim 1, characterized in that The content of the active material is 1 to 40 wt % based on the total mass of the hydrogenation catalyst.
5. A method for preparing the hydrogenation catalyst according to any one of claims 1 to 3, characterized in that: include: mixing the ammonium citrate solution and the nickel salt solution to obtain a metal organic complex solution; dispersing the carrier in a first solvent to obtain a first dispersion; mixing the first dispersion and the metal organic complex solution, and reacting to obtain a precursor; The precursor is calcined in a reducing atmosphere to obtain the hydrogenation catalyst.
6. The preparation method according to claim 5, characterized in that The molar ratio of ammonium citrate in the ammonium citrate solution to the nickel salt in the nickel salt solution is greater than 0 and less than or equal to 3; Preferably, the molar ratio of ammonium citrate in the ammonium citrate solution to the nickel salt in the nickel salt solution is greater than or equal to 1.5 and less than or equal to 2.5; Preferably, the first solvent comprises water and / or alcohol.
7. The preparation method according to claim 5, characterized in that The reducing atmosphere includes hydrogen; Preferably, the calcination temperature is 400-600° C. and the calcination time is 2-4 hours.
8. The preparation method according to claim 5, characterized in that The step of dispersing the carrier in the first solvent includes dispersing the carrier in the first solvent under ultrasonic conditions.
9. Use of the hydrogenation catalyst according to any one of claims 1 to 4 in hydrogenation, characterized in that: The hydrogenation catalyst is used to hydrogenate unsaturated molecules.
10. The use according to claim 9, characterized in that The unsaturated molecules include at least one of olefins, cycloolefins, aromatic hydrocarbons and condensed ring aromatic hydrocarbons; Preferably, the unsaturated molecule includes at least one of 1-hexene, toluene, quinoline, quinoline derivatives, naphthalene, naphthalene derivatives, fluorene, fluorene derivatives, dicyclopentadiene, dicyclopentadiene derivatives, norbornene, and norbornene derivatives.