Resin polyamine polyether demulsifier, composite resin polyamine polyether demulsifier and preparation method

Abstract

The invention discloses a resin polyamine polyether demulsifier, a composite resin polyamine polyether demulsifier and a preparation method. The organic amine is modified by the epoxy compound and then is subjected to cross-linking reaction with the epoxy resin in the presence of the basic catalyst by using the aromatic hydrocarbon as the solvent, the epoxy propane and the ethylene oxide are connected to synthesize the polyamine polyether, the reaction is low in energy consumption, short in time consumption and low in pollution, and the method is an effective method for replacing phenol amine resin polyether. The resin polyamine polyether is subjected to cross-linking modification to expand the molecular weight and is compounded to obtain the composite resin polyamine polyether demulsifier with wide molecular weight distribution and large molecular weight difference, and the demulsifier has higher applicability in complex oil fields and has certain advantages in the aspects of dehydration speed, dehydration rate and dehydrated water color.

Description

Technical Field

[0001] The present invention relates to the field of crude oil demulsifiers, and particularly to a resin polyamine polyether demulsifier, a composite resin polyamine polyether demulsifier and a preparation method thereof. Background Art

[0002] Crude oil demulsifiers are important chemical agents in crude oil production, gathering and transportation, and refining. Their main function is to cooperate with on-site process equipment to achieve the purpose of separating crude oil into oil and water, break the emulsion in crude oil, and make the treated crude oil meet the water content index. Among the many methods for realizing the separation of crude oil into oil and water, adding crude oil demulsifiers is a commonly used, economical and effective method. The composition of crude oil is complex, and there are natural surfactants such as asphaltenes, resins, and paraffins in crude oil. With the adoption of various enhanced oil recovery measures in oilfield production, the addition of various additives and surfactants has further increased the complexity of crude oil emulsions. The development of targeted demulsifiers is the key to ensuring oilfield production.

[0003] At present, the development of demulsifiers mainly focuses on polyethers based on poly (ethylene oxide - propylene oxide) copolymers, as well as their blends and cross - linked modified derivatives. The development of polyethers is the basis of demulsifiers, and the cross - linked modification method plays an important role in improving the performance of demulsifiers. At present, the development of polyethers for demulsifiers mainly focuses on the selection of polyether initiators, the ratio of propylene oxide to ethylene oxide, and the selection of block structures. The polyether initiators for demulsifiers mainly include higher alcohols, amine compounds, phenolic resin - based, and phenolic amine resin - based. Phenolic amine resin - based demulsifiers have advantages in the rapid dehydration of heavy oil and improving the quality of the purified oil of the treated crude oil. However, the synthesis process of the initiator of traditional phenolic amine resin demulsifiers is complex, the reaction conditions are harsh, the toxicity is high, and by - products are generated, increasing the production and environmental protection pressure. The newly developed resin polyamine polyether demulsifier not only has certain advantages in terms of dehydration speed, purified oil quality, and final water removal volume, but also simplifies the process in the resin synthesis of phenolic amine resin - based initiators, reduces production man - hours and energy consumption, and effectively controls pollution. Summary of the Invention

[0004] In order to solve the above - mentioned technical problems, the present invention provides a resin polyamine polyether demulsifier, a composite resin polyamine polyether demulsifier and a preparation method thereof. The production process is simple, with low energy consumption and low pollution. The prepared demulsifier has the characteristics of low dosing concentration, good dehydration effect, neat dehydration interface, and clear - colored dehydrated water.

[0005] In the first aspect, the present invention provides a preparation method of a resin polyamine polyether demulsifier, which is realized by the following technical solutions.

[0006] A preparation method of a resin polyamine polyether demulsifier includes the following steps:

[0007] S1. React an organic amine with an epoxide under vacuum at 120 - 150 °C to obtain intermediate A.

[0008] S2. Dissolve intermediate A in an aromatic hydrocarbon solvent and react it with an aromatic hydrocarbon solution of epoxy resin at 70 - 90 °C under the action of a basic catalyst to obtain resin polyamine initiator B.

[0009] S3. React resin polyamine initiator B with propylene oxide first under the condition of a basic catalyst to obtain resin polyamine oil head C, and then react it with ethylene oxide to obtain resin polyamine polyether D.

[0010] Further, in step S1, the organic amine is selected from one or more of diethanolamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine.

[0011] Further, in step S1, the epoxide is selected from propylene oxide and / or ethylene oxide.

[0012] Further, in step S1, the molar ratio of the organic amine to the epoxide is 1:(N - 1), where N is the number of active hydrogens on the nitrogen atom of the organic amine.

[0013] Further, in step S1, the reaction temperature of the organic amine and the epoxide is 120 - 150 °C, and the reaction pressure is < 0.4 MPa.

[0014] Further, in step S2, the aromatic hydrocarbon solvent is selected from crude C10 aromatic hydrocarbons.

[0015] Further, in step S2, the epoxy resin includes epoxy resin E51 and epoxy resin F51.

[0016] Further, in step S2, the mass ratio of intermediate A to the epoxy resin is 5:(0.05 - 4).

[0017] Further, in step S2, the epoxy resin is added dropwise to intermediate A, the dropping time is 0.5 - 1.5 hours, and the reaction is carried out for 1 - 2 hours after dropping.

[0018] Further, in step S3, the mass ratio of resin polyamine initiator B to propylene oxide is 1:(3 - 199); the mass ratio of resin polyamine oil head C to ethylene oxide is (1 - 9):(1 - 3).

[0019] Further, in step S3, the reaction temperature is controlled at 130 - 145 °C, and the reaction pressure is < 0.4 MPa.

[0020] Further, the basic catalyst is selected from potassium hydroxide, and the catalyst dosage accounts for 0.2% - 0.8% of the total mass of the reactants.

[0021] In a second aspect, the present invention provides a resin polyamine polyether demulsifier, which is achieved by the following technical solutions.

[0022] A resin polyamine polyether demulsifier prepared by the above method.

[0023] In a third aspect, the present invention provides a preparation method of a composite resin polyamine polyether demulsifier, which is achieved by the following technical solutions.

[0024] A preparation method of a composite resin polyamine polyether demulsifier includes the following steps:

[0025] Ⅰ. Dissolve the resin polyamine polyether D prepared by the above method in an aromatic solvent to prepare a resin polyamine demulsifier D-1;

[0026] Ⅱ. At 70 - 90 °C, add a basic catalyst to the resin polyamine polyether D prepared by the above method, dropwise add an ethylene glycol diglycidyl ether solution, react for 3 - 4 hours, and add an aromatic solvent to prepare a resin polyamine demulsifier D-2;

[0027] Ⅲ. Dissolve the resin polyamine polyether D prepared by the above method in an aromatic solution, at 80 - 100 °C, dropwise add an aromatic solution of toluene diisocyanate, react for 1 - 2 hours, and add an aromatic solvent to prepare a resin polyamine demulsifier D-3;

[0028] Ⅳ. Mix the resin polyamine demulsifier D-1, the resin polyamine demulsifier D-2, and the resin polyamine demulsifier D-3 in a mass ratio of 1:(1 - 2):(1 - 3) to obtain a composite resin polyamine polyether demulsifier.

[0029] By adopting the above technical solutions, after modifying the amine compound and crosslinking it with the epoxy resin, the problem that the direct reaction between the organic amine and the epoxy resin has too fast a reaction rate and is prone to curing is avoided. The synthesized polyether demulsifier has certain advantages in aspects such as dehydration speed, purified oil product, and final water removal amount. In order to be better applicable to multiple oil fields, the polyether synthesized from the above initiator is modified to increase the molecular weight and compounded, so that its molecular weight distribution span is large and the applicability is stronger. In addition, compared with the polyether demulsifier with a phenolic amine resin type initiator, the resin polyamine polyether demulsifier synthesized in this application has the characteristics of short reaction time, low reaction energy consumption, low pollution, and simple process. As the emulsification degree of the crude oil increases, the treatment difficulty increases, and the resin polyamine polyether demulsifier can be used as an alternative to the polyether demulsifier with a phenolic amine resin type initiator.

[0030] Further, in step Ⅰ, when the resin polyamine polyether D is dissolved in the aromatic solvent, the mass ratio of the aromatic solvent is 40% - 60%.

[0031] Further, in Step II, the dropping time of the ethylene glycol diglycidyl ether solution is 0.5 - 1 hour.

[0032] Further, in Step II, the mass ratio of the resin polyamine polyether D to the ethylene glycol diglycidyl ether is 100:(1 - 4).

[0033] Further, in Step III, the resin polyamine polyether D is dissolved in the aromatic hydrocarbon solution, and the pH is adjusted to 6 - 7.

[0034] Further, in Step III, the mass ratio of the resin polyamine polyether D to the toluene diisocyanate is 100:(1 - 4).

[0035] Further, in Step III, the dropping time of the aromatic hydrocarbon solution of the toluene diisocyanate is 0.5 - 1 hour.

[0036] Further, the aromatic hydrocarbon solvent is selected as the C10 crude aromatic hydrocarbon.

[0037] Further, the basic catalyst is selected as an organic tertiary amine or potassium hydroxide, and the catalyst dosage accounts for 0.2% - 0.5% of the total mass of the reactants.

[0038] Fourthly, the present invention provides a composite resin polyamine polyether demulsifier, which is achieved by the following technical solutions.

[0039] A composite resin polyamine polyether demulsifier prepared by the above method.

[0040] This application has the following beneficial effects.

[0041] The present invention uses the organic amine modified by the epoxy compound to crosslink with the epoxy resin under the condition of a basic catalyst to obtain a resin polyamine initiator, and then reacts with propylene oxide and ethylene oxide to synthesize a resin polyamine polyether demulsifier. Then, it is crosslinked and modified and compounded to form a composite resin polyamine polyether demulsifier with a wide molecular weight distribution and a large molecular weight difference. Compared with the prior art, this demulsifier has the advantages of wide applicability, low dosing concentration, good dehydration effect, neat dehydration interface, and clear dehydrated water color, and can further replace the phenolic amine polyether demulsifier. Specific Embodiments

[0042] The following further illustrates this patent application with reference to the embodiments.

[0043] Example 1

[0044] Add 100 g of tetraethylenepentamine to a high-temperature and high-pressure reactor, heat up to 90 °C and evacuate for 15 minutes, then continue to heat up to 130 °C and start feeding 184 g of propylene oxide. Control the reaction temperature at 140 ± 5 °C and the reaction pressure < 0.4 MPa. After the reaction is completed, cool down to 100 °C, add 6 g of potassium hydroxide aqueous solution (50%), stir for 30 minutes, and evacuate to dehydrate for 15 minutes; add 284 g of C10 crude aromatic hydrocarbons, keep the temperature at 90 °C, and dropwise add 189 g of C10 crude aromatic hydrocarbon solution (50%) of epoxy resin E51 over 1 hour. After the dropping is completed, continue the reaction for 2 hours to obtain initiator B (solid content 50%).

[0045] Take 75 g of initiator B, add 2.1 g of potassium hydroxide, heat up to 90 °C, evacuate for 15 minutes, then continue to heat up to 130 °C, and feed 713 g of propylene oxide. Control the reaction temperature at 140 ± 5 °C and the reaction pressure < 0.4 MPa. After the reaction is completed, prepare resin-based polyamine oil head C-01.

[0046] Place 500 g of oil head C-01 in the reactor, add 0.9 g of potassium hydroxide, evacuate at 90 °C, and feed ethylene oxide at 140 ± 5 °C, a total of 300 g. After the reaction is completed, discharge to obtain polyether D-01. Dissolve D-01 in C10 crude aromatic hydrocarbons to prepare demulsifier D-01A with an effective content of 50%;

[0047] Take 75 g of initiator B, add 7.5 g of potassium hydroxide, heat up to 90 °C, evacuate for 15 minutes, then continue to heat up to 130 °C, and feed 2512 g of propylene oxide. Control the reaction temperature at 140 ± 5 °C and the reaction pressure < 0.4 MPa. After the reaction is completed, prepare resin-based polyamine oil head C-02.

[0048] Place 670 g of oil head C-02 in the reactor, add 0.66 g of potassium hydroxide, evacuate at 90 °C, and feed ethylene oxide at 140 ± 5 °C, a total of 220 g. After the reaction is completed, discharge to obtain polyether D-02.

[0049] Take 100 g of D-02 at 70 °C, add 0.5 g of potassium hydroxide, stir evenly, then dropwise add 2 g of ethylene glycol diglycidyl ether over 1 hour, react for 3 hours, and add C10 crude aromatic hydrocarbon solvent to prepare resin-based polyamine demulsifier D-02A with an effective content of 50%;

[0050] Take 75 g of initiator B, add 4.1 g of potassium hydroxide, heat up to 90 °C, evacuate for 15 minutes, then continue to heat up to 130 °C, and feed 1388 g of propylene oxide. Control the reaction temperature at 140 ± 5 °C and the reaction pressure < 0.4 MPa. After the reaction is completed, prepare resin-based polyamine oil head C-03.

[0051] Place 370 g of oil head C-03 into a reaction kettle, add 0.3 g of potassium hydroxide, evacuate the air at 90 °C, introduce 120 g of ethylene oxide at 140 ± 5 °C. After the reaction is completed, the product discharged is polyether D-03.

[0052] Dissolve polyether D-03 in an aromatic hydrocarbon solution, add acetic acid to neutralize to pH 6. At 80 °C, dropwise add an aromatic hydrocarbon solution of toluene diisocyanate accounting for 2% of the polyether amount over 0.5 hours, and react for 2 hours to prepare a resin-based polyamine demulsifier D-03A with an effective content of 50%.

[0053] Mix D-01A, D-02A and D-03A evenly in a mass ratio of 1:2:2 to obtain a compound demulsifier DFP-01.

[0054] The masses of the above reaction materials are only for illustration. The specific masses can be adjusted proportionally according to the size of the reaction kettle and can be carried out step by step.

[0055] Performance test 1

[0056] For a comprehensive oil sample from a heavy oilfield in the Bohai Sea, at the on-site temperature, evaluate the performance of the synthesized demulsifier according to the requirements and steps in the "Technical Requirements and Inspection Specifications for Crude Oil Demulsifiers Q / HS2020", and observe the water separation amount, water separation speed, water color of the separated water and the water separation interface, etc. See Table 1 for details. (The demulsifier in use in this oilfield is a composite phenolic amine polyether demulsifier, that is, a compound of a phenolic amine polyether demulsifier and other conventional type initiator polyether demulsifiers)

[0057] Table 1

[0058]

[0059] Note: The index grading of the water color and interface in the experimental data is as follows:

[0060] Water color: A-, A, A+ - clear; B-, B, B+ - average; C-, C, C+ - poor

[0061] Interface: A-, A, A+ - neat; B-, B, B+ - average; C-, C, C+ - uneven

[0062] The performance evaluation results of the demulsifier synthesized in Example 1 show that after the demulsifier DFP-01 is modified by the modification method described in Example 1, its water separation speed, water separation rate and water color have been significantly improved. It shows that the polyether modification method of the present invention can improve the water separation performance of the demulsifier.

[0063] The embodiments of this specific implementation mode are all preferred embodiments of the present invention, and do not limit the protection scope of the present invention accordingly. Therefore, all equivalent changes made according to the structure, shape and principle of the present invention should be covered within the protection scope of the present invention.

Claims

1. A method for preparing a resin polyamine polyether demulsifier, characterized in that: The steps include: S1. Under vacuum and 120-150° C., an organic amine is reacted with an epoxy compound to prepare an intermediate A; S2. The intermediate A is dissolved in an aromatic solvent, and reacted with an epoxy resin aromatic solution at 70 to 90° C. under the action of an alkaline catalyst to prepare a resin polyamine initiator B; S3. The resin polyamine initiator B is first reacted with propylene oxide under alkaline catalyst conditions to obtain a resin polyamine oil head C, and then reacted with ethylene oxide to obtain a resin polyamine polyether D.

2. The method for preparing a resin polyamine polyether demulsifier according to claim 1, characterized in that: In step S1, the organic amine is selected from one or more of diethanolamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine.

3. The method for preparing a resin polyamine polyether demulsifier according to claim 1, characterized in that: In step S1, the epoxy compound is selected from propylene oxide and / or ethylene oxide.

4. The method for preparing a resin polyamine polyether demulsifier according to claim 1, characterized in that: In step S1, the molar ratio of the organic amine to the epoxy compound is 1:(N-1), where N is the number of active hydrogen atoms on the nitrogen atom of the organic amine.

5. The method for preparing a resin polyamine polyether demulsifier according to claim 1, characterized in that: In step S2, the epoxy resin includes epoxy resin E51 and epoxy resin F51.

6. The method for preparing a resin polyamine polyether demulsifier according to claim 1, characterized in that: In step S2, the mass ratio of the intermediate product A to the epoxy resin is 5:(0.05-4).

7. The method for preparing a resin polyamine polyether demulsifier according to claim 1, characterized in that: In step S3, the mass ratio of the resin polyamine initiator B to propylene oxide is 1:(3-199); the mass ratio of the resin polyamine oil head C to ethylene oxide is (1-9):(1-3).

8. A resin polyamine polyether demulsifier prepared by the method according to any one of claims 1 to 7.

9. A method for preparing a composite resin polyamine polyether demulsifier, characterized in that: The steps include: Ⅰ. The resin polyamine polyether D prepared by the method of any one of claims 1 to 7 is dissolved in an aromatic hydrocarbon solvent to prepare a resin polyamine demulsifier D-1; Ⅱ. The resin polyamine polyether D prepared by the method of any one of claims 1-7 is added with a basic catalyst at 70 to 90 ° C, ethylene glycol diglycidyl ether solution is added dropwise, reacted for 3 to 4 hours, and an aromatic solvent is added to prepare a resin polyamine demulsifier D-2; Ⅲ. The resin polyamine polyether D prepared by the method of any one of claims 1-7 is dissolved in an aromatic hydrocarbon solution, and an aromatic hydrocarbon solution of toluene diisocyanate is added dropwise at 80 to 100 ° C. The reaction is carried out for 1 to 2 hours, and an aromatic hydrocarbon solvent is added to prepare a resin polyamine demulsifier D-3; IV. The resin polyamine demulsifier D-1, the resin polyamine demulsifier D-2, and the resin polyamine demulsifier D-3 are mixed in a mass ratio of 1:(1-2):(1-3) to obtain a composite resin polyamine polyether demulsifier.

10. A composite resin polyamine polyether demulsifier prepared by the method of claim 9.

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