CN106753284B - A kind of viscosity reducer for crude oil and preparation method thereof - Google Patents

A kind of viscosity reducer for crude oil and preparation method thereof Download PDF

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Publication number
CN106753284B
CN106753284B CN201710006811.6A CN201710006811A CN106753284B CN 106753284 B CN106753284 B CN 106753284B CN 201710006811 A CN201710006811 A CN 201710006811A CN 106753284 B CN106753284 B CN 106753284B
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humic acid
crude oil
condensation
viscosity reducer
formulas
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CN106753284A (en
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黄诗哲
史学峰
王金本
杨惠
徐晓慧
吴亚芊
刘芳慧
陈刚
陈婷
樊明红
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Institute of Chemistry of CAS
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02Well-drilling compositions
    • C09K8/03Specific additives for general use in well-drilling compositions
    • C09K8/035Organic additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2618Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
    • C08G65/2633Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen the other compounds containing amide groups

Abstract

The present invention provides a kind of viscosity reducer for crude oil and preparation method thereof.The compound system that humic acid graft polyether modifier shown in the condensation product and Formula II of viscosity reducer for crude oil humic acid shown in Formulas I (HA) and triethylene glycol forms;Wherein, the mass ratio of humic acid graft polyether modifier shown in condensation product and Formula II shown in Formulas I is 20-40: 80-60.Viscosity reducer for crude oil provided by the present invention still has good viscosity reducing effect at high temperature, has emulsification and viscosity reduction ability well to crude oil.

Description

A kind of viscosity reducer for crude oil and preparation method thereof
Technical field
The invention belongs to viscosity reducer for crude oil technical fields, and in particular to a kind of viscosity reducer for crude oil and preparation method thereof.
Background technique
Viscous crude resource has become important one of the strategic making & breaking in China, causes to exploit because its density is big, viscosity is high And difficulty of transportation, it is difficult to exploit.Chemical viscosity reduction technology is that current viscosity reduction amplitude is maximum and use most economical one of measure, And it is widely used in each viscous crude field in the world.The effects of chemical viscosity reduction agent can be effectively disperseed, emulsify for viscous crude shows Writing reduces viscosity of thickened oil, reduces viscous crude flow resistance in stratum and pit shaft, this is for reducing recovery process energy consumption, reducing and discharge Pollution, raising thick oil recovery ratio are of great significance.
Humic acid is product of the natural plant residuum after rotting to decompose, and is that a kind of natural macromolecular of complexity is organic Matter.Its intramolecular contains the various actives such as carbonyl, carboxyl, alcoholic extract hydroxyl group and phenolic hydroxyl group functional group, make it have acidity, hydrophily, Interfacial activity, cation exchange capacity (CEC), complexing and absorption dispersibility, thus humic acid substance is opened in environmental protection, petroleum It adopts, fields such as agricultural gardening, medicine, analytical chemistry, battery industry etc. all have a wide range of applications.
Summary of the invention
The object of the present invention is to provide a kind of viscosity reducer for crude oil and preparation method thereof.
Viscosity reducer for crude oil provided by the present invention is the condensation product and Formula II of the humic acid as shown in Formulas I (HA) Yu triethylene glycol The compound system of shown humic acid graft polyether modifier composition;Wherein, the condensation product of humic acid and triethylene glycol shown in Formulas I and The mass ratio of the modifier of humic acid graft polyether shown in Formula II is 20-40: 80-60, preferably 30-40: 70-60, concretely 40: 60 or 30: 70,
In Formulas I, n indicates condensation degree, and n is the integer of 1-100, preferably 1-20, concretely 5,10,15 or 20;
In Formula II, x is the integer of 20-80, preferably 40-80, concretely 50 or 70;Y is the integer of 10-40, preferably 20- 40, concretely 30;
In Formulas I, Formula II, HA indicates that humic acid, structural formula are as follows:
Humic acid is a kind of mixture of unformed macromolecular of complexity, and the humic acid of separate sources also has very in structure Big difference, so there are no an accurate unified conclusions for structure of the people to humic acid at present, only to work contained thereon Property group reached common recognition, this structural formula be deduce come humic acid a kind of possible structural model, R is also uncertain 's.
The condensation product of humic acid shown in above-mentioned Formulas I (HA) and triethylene glycol is that method as steps described below is prepared : with triphenyl phosphorus (PPh3) and diethyl azodiformate (DEAD) be catalyst so that triethylene glycol and humic acid carry out Condensation reaction obtains the condensation product of (HA) and triethylene glycol of humic acid shown in Formulas I.
Wherein, the mass ratio of triethylene glycol and humic acid is 1:5-15, concretely 1:10.
The temperature of the condensation reaction is 140-160 DEG C, time 2-6h, concretely 3h.
Humic acid graft polyether modifier shown in above-mentioned Formula II is prepared by the method comprising the following steps:
Using humic acid as initiator, using KOH as catalyst, under inert gas protection, successively with propylene oxide (PO) and Ethylene oxide (EO) carry out ring-opening polymerization to get.
Wherein, the mass ratio of humic acid and epoxide can be 1:5~15, the mass ratio of propylene oxide and ethylene oxide It can be 3~1:1.
The temperature of the ring-opening polymerization is 120~140 DEG C, and pressure is 0.2~0.4MPa, and the time is 2~10h.
Viscosity reducer for crude oil provided by the present invention is prepared by the method comprising the following steps:
Humic acid graft polyether modifier shown in the condensation product and Formula II of humic acid shown in Formulas I (HA) and triethylene glycol is mixed It is even, obtain viscosity reducer for crude oil.
Wherein, humic acid graft polyether shown in the condensation product and Formula II of humic acid shown in Formulas I (HA) and triethylene glycol is modified The mass ratio of object is 20-40: 80-60, preferably 30-40: 70-60, concretely 40: 60 or 30: 70.
Application of the above-mentioned viscosity reducer for crude oil in oil extraction also belongs to protection scope of the present invention.
Viscosity reducer for crude oil provided by the invention still has good viscosity reducing effect at high temperature, has good emulsification to crude oil With viscosity reduction ability.
Detailed description of the invention
Viscosity reducer for crude oil made from Fig. 1 1- of embodiment of the present invention embodiment 4 is 3 × 104Mg/L salinity salt water medium viscosity With the relation curve (25 DEG C of measuring temperature) of concentration.
Fig. 2 is viscosity reducer for crude oil made from 1- of embodiment of the present invention embodiment 43 × 104It is glued in mg/L salinity salt water The relation curve (test concentrations 1000mg/L) of degree and temperature.
Specific embodiment
The present invention will be described below by way of specific embodiments, but the present invention is not limited thereto.
Experimental method used in following embodiments is conventional method unless otherwise specified;Institute in following embodiments Reagent, material etc., are commercially available unless otherwise specified.
The condensation product of humic acid shown in Formulas I as used in the following examples (HA) and triethylene glycol is according to including following steps What rapid method was prepared: by triethylene glycol, the concentrated sulfuric acid, triphenyl phosphorus (PPh3) and diethyl azodiformate (DEAD) plus Enter into water segregator, reflux water-dividing, humic acid solution is slowly included in by constant pressure funnel, after 60 DEG C are stirred 1 hour, heating To 180 DEG C of reaction 3h.Filtering is washed, and is separated, recrystallization, is repeated above step and is obtained condensation product shown in Formulas I.Specific investment is former Doses and the related table of condensation degree n are as follows:
Humic acid Triethylene glycol The concentrated sulfuric acid Triphenyl phosphorus Diethyl azodiformate
N=5 20g 2g 1ml 2g 0.5g
N=10 50g 5g 2.5ml 5g 1.2g
N=15 70g 7g 3.5ml 7g 1.8g
N=20 90g 9g 1ml 2g 0.5g
Humic acid graft polyether modifier shown in Formula II as used in the following examples is according to the side included the following steps What method was prepared: humic acid and catalyst KOH being added in autoclave, 115 ± 5 DEG C is warming up to, is purged with nitrogen Displacement three times, adds propylene oxide, and controlling gross pressure in reaction kettle is 0.2~0.4MPa, 140 ± 5 DEG C of reaction temperature, to anti- After answering in kettle pressure to fall after rise, the reaction was continued 60min.Ethylene oxide is added, control reacting kettle inner pressure is lower than 0.4MPa, continues anti- Answer 60min.After temperature of reaction system is brought down below 80 DEG C, product is taken out.The related table for putting into material quantity and x, y is as follows:
Humic acid Propylene oxide Ethylene oxide Potassium hydroxide
X=50, y=30 20g 100g 50g 10g
X=70, y=30 20g 160g 70g 10g
The preparation of embodiment 1, viscosity reducer for crude oil A
By the condensation product of humic acid shown in 40g Formulas I (HA) and triethylene glycol, (wherein, condensation degree n is 5), shown in 60g Formula II Humic acid graft polyether modifier (x 50, y 30) mixing, obtains viscosity reducer for crude oil A.
The preparation of embodiment 2, viscosity reducer for crude oil B
By the condensation product of humic acid shown in 30g Formulas I (HA) and triethylene glycol (wherein, condensation degree n for 10), 70g Formula II institute Show that humic acid graft polyether modifier (x 50, y 30) is mixed, obtains viscosity reducer for crude oil B.
The preparation of embodiment 3, viscosity reducer for crude oil C
By the condensation product of humic acid shown in 40g Formulas I (HA) and triethylene glycol (wherein, condensation degree n for 15), 60g Formula II institute Show that humic acid graft polyether modifier (x 70, y 30) is mixed, obtains viscosity reducer for crude oil C.
The preparation of embodiment 4, viscosity reducer for crude oil D
By the condensation product of humic acid shown in 30g Formulas I (HA) and triethylene glycol (wherein, condensation degree n for 20), 70g Formula II institute Show that humic acid graft polyether modifier (x 70, y 30) is mixed, obtains viscosity reducer for crude oil D.
Measure embodiment
Measure example 1
4 kinds of viscosity reducer for crude oil (A, B, C and D) of Examples 1 to 4 preparation are used into salinity 3 × 104The salt moisture of mg/L It is not formulated as the reducing crude oil viscosity agent solution of various concentration, measures solution concentration, the relationship of temperature and viscosity, the result is shown in Figure 1 and figure 2。
Measure example 2
The reducing crude oil viscosity agent solution for the use of the concentration prepared in measurement example 1 being 1000mg/L, in the case where temperature is 25 DEG C, respectively It is added in the tool plug test tube equipped with 50ml dehydration degassing viscous crude sample, solution and viscous crude sample volume ratio are 1:1.Cover tightly test tube After plug, test tube is placed in oscillation case, horizontal oscillations 80-100 times, amplitude should be greater than 20cm, after being sufficiently mixed, use The viscosity of Brookfield viscosity meter mixed system.The results are shown in Table 1 for reducing thick oil viscosity.
The reducing thick oil viscosity effect of 1 viscosity reducer for crude oil of table
Sample Viscosity (mPas) Reduction rate of crude oil viscosity (%)
Blank 1800 --
A 423 77
B 322 82
C 180 90
D 277 85
As can be seen from Table 1, after viscosity reducer for crude oil being added, system viscosity is greatly lowered, and reducing thick oil viscosity rate is above 75%.Wherein the reducing thick oil viscosity effect of viscosity reducer for crude oil C is the most obvious, and viscosity break ratio can achieve 90%.

Claims (7)

1. a kind of viscosity reducer for crude oil, the grafting of humic acid shown in the condensation product and Formula II of humic acid and triethylene glycol as shown in Formulas I is poly- Ether modifier composition, wherein humic acid graft polyether shown in the condensation product and Formula II of humic acid and triethylene glycol shown in Formulas I is modified The mass ratio of object is 20-40: 80-60;
In Formulas I, n indicates that condensation degree, n are the integer of 1-20, and HA indicates humic acid;
In Formula II, x is the integer of 40-80;Y is the integer of 20-40, and HA indicates humic acid.
2. viscosity reducer for crude oil according to claim 1, it is characterised in that: humic acid shown in Formulas I and three second in claim 1 The condensation product of glycol is that method as steps described below is prepared: with triphenyl phosphorus and diethyl azodiformate for catalysis Agent obtains the condensation product of humic acid and triethylene glycol shown in Formulas I so that triethylene glycol and humic acid carry out condensation reaction.
3. viscosity reducer for crude oil according to claim 2, it is characterised in that: the mass ratio of triethylene glycol and humic acid is 1:5- 15;
The temperature of the condensation reaction is 140-160 DEG C, and the time of the reaction is 2-6h.
4. viscosity reducer for crude oil according to claim 1, it is characterised in that: humic acid shown in Formula II is grafted in claim 1 Polyether-modified object is prepared by the method comprising the following steps:
Using humic acid as initiator, using KOH as catalyst, under inert gas shielding, successively with propylene oxide and ethylene oxide into Row ring-opening polymerization to get.
5. viscosity reducer for crude oil according to claim 4, it is characterised in that: the mass ratio of humic acid and epoxide is 1: 5~15, the mass ratio of propylene oxide and ethylene oxide is 3~1:1;
The temperature of the ring-opening polymerization is 120~140 DEG C, and pressure is 0.2~0.4MPa, and the time is 2~10h.
6. a kind of method for preparing viscosity reducer for crude oil of any of claims 1-5, includes the following steps: to want right Ask in 1 the condensation product of humic acid and triethylene glycol shown in Formulas I with and claim 1 in humic acid graft polyether modification shown in Formula II Object mixes.
7. application of the viscosity reducer for crude oil of any of claims 1-5 in oil extraction.
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CN107118756B (en) * 2017-06-19 2019-08-20 中国海洋石油集团有限公司 A kind of efficient thick-oil thinner and preparation method thereof
CN109181670B (en) * 2018-09-07 2020-06-09 中国科学院化学研究所 Efficient thick oil viscosity reducer and preparation method thereof
CN110041904A (en) * 2019-04-23 2019-07-23 中国海洋石油集团有限公司 Humic acid and alkylamine Compositional type heavy crude thinner and the preparation method and application thereof
CN110305325A (en) * 2019-07-22 2019-10-08 陕西科技大学 Humic acid polyethyleneglycol-graft copolymer and preparation method thereof

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