1. A catalyst composition is characterized by comprising the following components in percentage by mass: 1-4 wt% of free azacarbene, 1-2 wt% of azacarbene iron, 15-30 wt% of phase transfer catalyst, 1-5 wt% of hydrogen donor, 5-10 wt% of phosphoric acid, 0.5-1 wt% of emulsifier, and the balance of solvent, wherein the total amount is 100%.

2. The catalyst composition of claim 1, further comprising 5-10% styrene tar.

3. The catalyst composition of claim 1, wherein the hydrogen donor is methanol.

4. The catalyst composition of claim 1, wherein the solvent is benzene.

5. The catalyst composition of claim 1 wherein the emulsifier is span 80.

6. The catalyst composition of claim 1, wherein the phase transfer catalyst is a quaternary ammonium salt.

7. The catalyst composition of claim 6, wherein the quaternary ammonium salt comprises one or both of benzyltriethylammonium chloride and ammonium bromide.

8. A method of preparing the catalyst composition of any one of claims 1 to 7, comprising: mixing free azacarbene and azacarbene iron with a solvent according to the proportion, then adding a phase transfer catalyst and a hydrogen donor for continuous mixing, and then adding phosphoric acid and an emulsifier for mixing to obtain the catalyst composition.

9. The method of claim 8, further comprising adding styrene tar for mixing before adding the phase transfer catalyst and the hydrogen donor for further mixing.

10. Use of the catalyst composition according to any one of claims 1 to 7 or the catalyst composition prepared by the preparation method according to any one of claims 8 to 9 for treating heavy oil.

Background

The viscous oil has the characteristics of high viscosity, high condensation point, poor fluidity in stratum and the like, so that the viscous oil is difficult to effectively exploit by adopting a conventional method. At present, heavy oil recovery technologies mainly comprise cold recovery technologies, hot recovery technologies and composite recovery technologies combining cold recovery and hot recovery. Among these mining techniques, the thermal mining technique mainly based on steam injection is most widely used.

In order to ensure the safety in the air injection oil extraction process and improve the economy of the oil extraction process, the university of southwest petroleum group in 2002 provides a heavy oil reservoir air injection low-temperature catalytic oxidation oil extraction technology, which is characterized in that in the process of injecting air to produce heavy oil under the oil reservoir condition, a proper catalyst is injected to improve the low-temperature oxidation rate of crude oil, increase oxygen consumption and release heat, and simultaneously, flue gas or nitrogen is formed to assist in injecting high-dryness steam externally to improve the recovery rate of the heavy oil, thereby effectively improving the formation energy, being environment-friendly, having low cost, high heat utilization rate and the like. However, the safety problem of the low-temperature catalytic oxidation technology for injecting air into thick oil has been the focus of academic attention, especially the safety of a production well, and the O in the produced gas must be ensured when the air breaks through₂Is below the explosion safety threshold (5%). For this reason, the current trend is to oxidize the source O₂By replacement with organic hydrogen peroxide compounds, H₂O₂、KIO₄、NaIO₄And the like, with or without the addition of a solvent, assisted by a catalyst. However, the existing catalyst for catalytic oxidation for thick oil exploitation and viscosity reducer thereof still have the problems of low catalytic viscosity reduction efficiency and high heavy component content in the thickened oil after viscosity reduction.

The conventional thick oil air-injection low-temperature catalytic oxidation catalysts such as oil-soluble metal salts, nano metal catalysts, bifunctional catalysts and the like have the problems of low catalytic effect, easy agglomeration, high preparation cost and the like to different degrees, and the key for solving the technical problem is to obtain a proper low-temperature oxidation viscosity reducer.

Disclosure of Invention

The invention aims to overcome the technical defects, provides a catalyst composition, and a preparation method and application thereof, and solves the technical problems of high cost and poor viscosity reducing effect of the catalyst in the prior art.

In order to achieve the technical purpose, the technical scheme of the invention provides a catalyst composition and a preparation method and application thereof.

The invention provides a catalyst composition, which comprises the following components in percentage by mass: 1-4 wt% of free azacarbene, 1-2 wt% of azacarbene iron, 15-30 wt% of phase transfer catalyst, 1-5 wt% of hydrogen donor, 5-10 wt% of phosphoric acid, 0.5-1 wt% of emulsifier, and the balance of solvent, wherein the total amount is 100%.

Further, the paint also comprises 5-10% of styrene tar.

Further, the hydrogen donor is methanol.

Further, the solvent is benzene.

Further, the emulsifier is span 80.

Further, the phase transfer catalyst is a quaternary ammonium salt.

Further, the quaternary ammonium salt comprises one or two of benzyltriethylammonium chloride and ammonium bromide.

The invention also provides a preparation method of the catalyst composition, which comprises the following steps: mixing free azacarbene and azacarbene iron with a solvent according to the proportion, then adding a phase transfer catalyst and a hydrogen donor for continuous mixing, and then adding phosphoric acid and an emulsifier for mixing to obtain the catalyst composition.

Further, adding styrene tar for mixing before adding the phase transfer catalyst and the hydrogen donor for further mixing.

In addition, the invention also provides an application of the catalyst composition or the catalyst composition prepared by the preparation method in treating thick oil.

Compared with the prior art, the invention has the beneficial effects that: the phase transfer catalyst can bring azacarbene iron into thick oil to contact with the oil, phosphoric acid provides protons, an emulsifier promotes the thick oil to form water-in-oil to facilitate viscosity reduction, the thick oil releases metal ions complexed with the thick oil in the viscosity reduction process, the metal ions and free azacarbene form stable carbon-metal bonds to obtain a stable complex, the complex and the azacarbene iron perform chemical reaction to reduce viscosity, the metal ions released by the thick oil can be utilized to react to reduce the viscosity while reducing the viscosity, so that the fast and efficient viscosity reduction of the thick oil can be realized by only needing less azacarbene iron and free azacarbene, and the viscosity reduction rate of the thick oil can be up to more than 90% after 6-hour viscosity reduction treatment.

Drawings

FIG. 1 is a chemical structure identification NMR chart of free azacarbene of the present invention;

FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the chemical structure identification of the azacarbene iron of the invention.

Detailed Description

The specific embodiment provides a catalyst composition, which comprises the following components in percentage by mass: 1-4 wt% of free azacarbene, 1-2 wt% of azacarbene iron, 15-30 wt% of phase transfer catalyst, 1-5 wt% of hydrogen donor, 5-10 wt% of phosphoric acid, 0.5-1 wt% of emulsifier, and the balance of solvent, wherein the total amount is 100%; the hydrogen donor is methanol; the solvent is benzene; the emulsifier is span 80; the phase transfer catalyst is quaternary ammonium salt; further, the quaternary ammonium salt includes one or both of benzyltriethylammonium chloride and ammonium bromide.

In certain embodiments, the catalyst composition further comprises 5-10% styrene tar. The styrene tar is the rectification residue produced in the production process of preparing styrene by ethylbenzene dehydrogenation, and the main components of the styrene tar are styrene polymer, styrene, derivatives and the like. The styrene tar contains a large amount of mixed aromatic hydrocarbon components, can be dissolved in the thick oil, has a diluting effect on the thick oil, and is favorable for promoting the contact of the azacarbene iron and the free azacarbene with the thick oil, so as to promote viscosity reduction.

The embodiment also comprises a preparation method of the catalyst composition, which comprises the following steps: mixing free azacarbene and azacarbene iron with a solvent according to the proportion, then adding a phase transfer catalyst and a hydrogen donor for continuous mixing, and then adding phosphoric acid and an emulsifier for mixing to obtain the catalyst composition.

In certain embodiments, the method further comprises adding styrene tar for mixing before adding the phase transfer catalyst and the hydrogen donor for further mixing.

The specific embodiment also comprises the application of the catalyst composition in treating the thick oil, and specifically comprises the steps of adding water into the thick oil according to the mass ratio of the water to the thick oil (2-3) to (7-8), and then adding the catalyst composition into the thick oil according to the addition amount of the catalyst composition being 0.5-2.0% of the mass of the thick oil for viscosity reduction.

The structural formula of the free azacarbene in the present embodiment is as follows:

the structural formula of the azacarbene in the present embodiment is:

the free azacarbene in the present embodiment is prepared by the following steps:

adding 2, 6-diisopropylaniline, 40% glyoxal and formic acid into absolute ethyl alcohol for reaction for 2d, filtering, and washing with cold methanol to obtain the diaza-butadiene; wherein the molar ratio of the 2, 6-diisopropylaniline to the glyoxal is 2: 1; the yield of diazabetadine was 89.2%;

stirring paraformaldehyde and HCl (4M in dioxane) at 30 ℃ for 12 hours, then adding a mixture of diazadiene and THF, continuously stirring at room temperature for reacting for 4 hours, and filtering and washing to obtain the 1, 3-bis (2, 6-diisopropyl-1-phenyl) imidazolium chloride; the molar ratio of the diazabetadine, the paraformaldehyde, and the HCl is 1:1: 1; the yield of 1, 3-bis (2, 6-diisopropyl-1-phenyl) imidazolium chloride was 88.4%;

mixing 1, 3-bis (2, 6-diisopropyl-1-phenyl) imidazolium chloride and potassium tert-butoxide according to a molar ratio of 1:1, adding the mixture into a first organic solvent THF, stirring and reacting for 4 hours at room temperature, extracting by ethyl acetate, drying and purifying to obtain the free aza-carbene; the yield of free azacarbene is 66.7%; in FIG. 1, the free azacarbene 1H-NMR (400MHz, C6D6) is D1.13 (D, J ═ 9.2Hz,12H, CH (CH)₃)₂),1.23(d,J＝9.2Hz,12H,CH(CH₃)₂),2.91(sep,J＝9.2Hz,4H,CH(CH₃)₂),6.57(s,2H,NCH),7.11(m,4H,m-C₆H₃),7.22(m,2H,p-C₆H₃)。

Further, the azacarbene iron of the present embodiment is prepared by the following steps:

free azacarbene and anhydrous FeCl₃Adding the mixture into a second organic solvent THF according to the molar ratio of 1:1, stirring at room temperature for 30min, then carrying out vacuum drying, filtering and washing by using a mixed solution of toluene and pentane, and then recrystallizing by using a mixed solution of THF and pentane to obtain azacarbene-ferric, wherein the yield of the azacarbene-ferric is 57.6%; in FIG. 2, the azacarbene iron [ FeCl ]₃(IPr)]¹H NMR(C6D6):δ8.55(24H,CH₃),1.51(4H，＝CH),0.46(8H,CHMe₂),-2.20(8H,m-H),-2.89(24H,CH₃),-3.68(4H,p-H).μ_eff(Evans,C₆D₆):7.4(1)Μb.μ_eff(Evans,C₆D₆):5.8(1)μ_B.Anal.Calcd for C₂₇H₃₆Cl₃FeN₂:C,58.88；H,6.59；N,5.09.Found:C,57.54；H,6.61；N,4.67。

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

In the following examples, the catalyst compositions of examples 1-4 were prepared according to the following procedure:

mixing free azacarbene and azacarbene iron with a solvent according to the proportion, then adding a phase transfer catalyst and a hydrogen donor for continuous mixing, and then adding phosphoric acid and an emulsifier for mixing to obtain the catalyst composition.

The catalyst compositions of examples 5-7 were prepared according to the following procedure:

mixing free azacarbene and azacarbene iron with a solvent according to a ratio, adding styrene tar for mixing, adding a phase transfer catalyst and a hydrogen donor for continuously mixing, and adding phosphoric acid and an emulsifier for mixing to obtain the catalyst composition.

Example 1

This example provides a catalyst composition, which includes, by mass: 2 wt% of free azacarbene, 2 wt% of azacarbene iron, 20 wt% of phase transfer catalyst benzyltriethylammonium chloride, 3 wt% of hydrogen donor methanol, 5 wt% of phosphoric acid, 800.6 wt% of emulsifier span and the balance of solvent benzene, wherein the total amount is 100%.

Example 2

The embodiment provides a catalyst composition, which comprises the following components in percentage by mass: 1 wt% of free azacarbene, 2 wt% of azacarbene iron, 30 wt% of phase transfer catalyst ammonium bromide, 1 wt% of hydrogen donor methanol, 8 wt% of phosphoric acid, 800.8 wt% of emulsifier span and the balance of solvent benzene, wherein the total amount is 100%.

Example 3

The embodiment provides a catalyst composition, which comprises the following components in percentage by mass: 4 wt% of free azacarbene, 1 wt% of azacarbene iron, 15 wt% of benzyl triethyl ammonium chloride serving as a phase transfer catalyst, 5 wt% of methanol serving as a hydrogen donor, 10 wt% of phosphoric acid, 801 wt% of emulsifier span and the balance of benzene serving as a solvent, wherein the total amount is 100%.

Example 4

The embodiment provides a catalyst composition, which comprises the following components in percentage by mass: 3 wt% of free azacarbene, 2 wt% of azacarbene iron, 20 wt% of phase transfer catalyst ammonium bromide, 2 wt% of hydrogen donor methanol, 8 wt% of phosphoric acid, 800.5 wt% of emulsifier span, and the balance of solvent benzene, wherein the total amount is 100%.

Example 5

This example provides a catalyst composition, which includes, by mass: 2 wt% of free azacarbene, 2 wt% of azacarbene iron, 20 wt% of benzyl triethyl ammonium chloride serving as a phase transfer catalyst, 3 wt% of methanol serving as a hydrogen donor, 5 wt% of phosphoric acid, 800.6 wt% of span serving as an emulsifier, 5 wt% of styrene tar and the balance of benzene serving as a solvent, wherein the total amount is 100%.

Example 6

The embodiment provides a catalyst composition, which comprises the following components in percentage by mass: 1 wt% of free azacarbene, 2 wt% of azacarbene iron, 30 wt% of phase transfer catalyst ammonium bromide, 1 wt% of hydrogen donor methanol, 8 wt% of phosphoric acid, 800.8 wt% of emulsifier span, 8 wt% of ethylene tar and the balance of solvent benzene, wherein the total amount is 100%.

Example 7

The embodiment provides a catalyst composition, which comprises the following components in percentage by mass: 4 wt% of free azacarbene, 1 wt% of azacarbene iron, 15 wt% of benzyl triethyl ammonium chloride serving as a phase transfer catalyst, 5 wt% of methanol serving as a hydrogen donor, 10 wt% of phosphoric acid, 801 wt% of span serving as an emulsifier, 10 wt% of ethylene tar and the balance of benzene serving as a solvent, wherein the total amount is 100%.

Comparative example 1

The catalyst composition proposed in this comparative example differs from example 1 in that it does not contain azacarbene iron, and specifically comprises, in mass percent: 2 wt% of free azacarbene, 20 wt% of benzyl triethyl ammonium chloride serving as a phase transfer catalyst, 3 wt% of hydrogen donor methanol, 5 wt% of phosphoric acid, 800.6 wt% of span serving as an emulsifier, and the balance of benzene serving as a solvent, wherein the total amount is 100%.

Comparative example 2

The catalyst composition proposed in the present comparative example differs from example 1 in that it does not contain free azacarbene, and specifically comprises, in mass percent: 2 wt% of azacarbene iron, 20 wt% of benzyltriethylammonium chloride serving as a phase transfer catalyst, 3 wt% of methanol serving as a hydrogen donor, 5 wt% of phosphoric acid, 800.6 wt% of span serving as an emulsifier, and the balance of benzene serving as a solvent, wherein the total amount is 100%.

Comparative example 3

The catalyst composition proposed in this comparative example differs from example 1 in that it does not contain free azacarbene and azacarbene iron, and specifically comprises, in mass percent: 20 wt% of phase transfer catalyst benzyltriethylammonium chloride, 3 wt% of hydrogen donor methanol, 5 wt% of phosphoric acid, 800.6 wt% of emulsifier span and the balance of solvent benzene, wherein the total amount is 100%.

Comparative example 4

The catalyst composition proposed in this comparative example differs from example 5 in that it does not contain free azacarbene and azacarbene iron, and specifically comprises, in mass percent: 20 wt% of phase transfer catalyst benzyltriethylammonium chloride, 3 wt% of hydrogen donor methanol, 5 wt% of phosphoric acid, 800.6 wt% of emulsifier span, 5 wt% of styrene tar and the balance of solvent benzene, wherein the total amount is 100%.

Application example

The catalyst compositions proposed in examples 1 to 7 and comparative examples 1 to 3 were used to treat thick oil produced from Touha as a reactant (viscosity of 95650 mPas at 50 ℃); specifically, the thickened oil and water are mixed according to the mass ratio of 7:3, then the catalyst composition is added into the thickened oil according to the addition amount of the catalyst composition being 1.0% of the mass of the thickened oil, viscosity reduction is carried out at 60 ℃, and the viscosity reduction rate of 4h, 6h and 8h is detected and obtained.

The viscosity value of the thick oil was measured to evaluate the catalytic performance of the catalyst. The viscosity reduction rate is calculated by a formula of delta eta (%) - (eta 0-eta)/eta 0) multiplied by 100%, wherein eta 0 and eta respectively refer to the viscosity of the oil sample before and after reaction and have the unit of mPa & s; the results of reducing caking are shown in table 1.

TABLE 1 reduced cohesiveness fruits for thickened oils at different times in examples 1-7 and comparative examples 1-3

As can be seen from Table 1, the viscosity reducing rate of the example 1-4 after 8 hours is as high as about 90%, and the viscosity reducing rate of the example 5-7 is as high as about 90% because the ethylene tar is added to improve the fluidity of the thick oil and obviously accelerate the viscosity reducing speed, only 6 hours are needed; whereas comparative examples 1-2 had very low viscosity reduction, probably because the content of azacarbene iron or free azacarbene in the comparative examples was low, and small amounts of azacarbene iron and free azacarbene alone did not contribute to viscosity reduction; in addition, the proportion of the heavy components cracked into light components in the examples 1 to 7 is up to more than 70 percent, which is obviously higher than that in the comparative examples 1 to 3; comparative examples 1-3 also further illustrate that the viscosity reducing effect of the catalyst composition of the present invention is achieved by the combination of the components.

The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.