CN1133486C - Lignin sulfonate surfactant for oil field, its preparation process and use in tertiary oil recovery - Google Patents

Lignin sulfonate surfactant for oil field, its preparation process and use in tertiary oil recovery Download PDF

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CN1133486C
CN1133486C CNB99107579XA CN99107579A CN1133486C CN 1133486 C CN1133486 C CN 1133486C CN B99107579X A CNB99107579X A CN B99107579XA CN 99107579 A CN99107579 A CN 99107579A CN 1133486 C CN1133486 C CN 1133486C
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lignosulfonate
lignosulphonate
oil
temperature
phenol
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CN1275430A (en
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陈惠琴
杨玉哲
吴军政
徐艳妹
伍晓林
张潞光
李道山
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Daqing Petroleum Administration Bureau
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Abstract

The present invention relates to a lignosulfonate surfactant for an oil field, a preparation method thereof and an application thereof in tertiary oil recovery, alkali paper-manufacturing waste liquid lignin and phenol are used as raw materials, and the lignin is modified and sulfonated by a condensation reaction method to obtain modified lignosulfonate. The performance of the surface and the interface of the lignosulphonate can be greatly enhanced, and the lignosulphonate has good synergistic effect when the lignosulphonate is mixed with an alkyl sulfonate type surfactant. The lignosulphonate can form the ultra low interfacial tension of the order of the magnitude of 10<-3> mN/m with crude oil in the wide ranges of an active agent, alkali and the degree of mineralization, and compared with the displacement efficiency of water drive, the displacement efficiency of the lignosulfonate is enhanced by more than 15% 00IP according to the result of a displacement test. Compared with pure alkyl sulfonate, the lignosulfonate saves 30 to 60% of cost, and the lignosulfonate as a mixing preparation can be well used for the tertiary oil recovery.

Description

Lignosulfonate surfactant for oil field, preparation method thereof and application thereof in tertiary oil recovery
Technical Field
The invention relates to a surfactant for oil field (oil displacement), its preparation and application, in particular to an alkylbenzene sulfonate surfactant for oil field, its preparation method and its application as a compound agent in tertiary oil recovery.
Background
When the oil field enters a high water-content oil production stage, in order to further improve the oil extraction efficiency and meet the requirements of industrial production, the tertiary oil extraction technology plays an important role in ensuring the stability and high yield of the oil field. Around tertiary oil recovery technology, the ternary combination flooding method has been widely adopted and achieves good effects. At present, various matching technologies of the technology become mature, but the cost is further reduced, so that the economic clearance of the ternary combination flooding is a main public target of the technology, and the development of novel, efficient and cheap oil displacement agents is urgent.
Lignin is a by-product produced in paper making, and is usually discharged in the form of waste liquid, which is not only a waste of resources, but also a certain pollution to the environment. Therefore, the method has certain economic and social benefits for fully utilizing the waste water. The annual production of paper pulp in China is more than 600 million tons, wherein the alkaline papermaking accounts for 70-75%, so that the alkali lignin has wide sources and low price and can meet the requirement of tertiary oil recovery to a certain extent.
Disclosure of Invention
The invention aims to provide a novel, efficient and low-cost lignosulfonate surfactant which can be applied to oil fields;
another object of the present invention is to provide a simple and practical method for preparing the above lignosulfonate surfactant;
the invention also aims to provide the application of the lignosulfonate surfactant as a compound agent in the ternary combination flooding in tertiary oil recovery.
In order to achieve the purpose of the invention, the invention provides a modified lignosulfonate.
The conventional lignosulfonate is the most commonly used surfactant, but because of its poor surface activity, it is mainly used as a dispersant for liquid-solid dispersion systems, and usually, the surface tension of its aqueous solution is about 50mN/m, and the critical micelle concentration is high. For these reasons, it is difficultto reduce the oil-water interfacial tension by using a common lignosulfonate, and it is necessary to modify the lignosulfonate. In view of the fact that lignosulfonates have too high a water solubility, lipophilic components are introduced into the structure.
Lignin has the following structural units:
because of the existence of the phenolic hydroxyl, not only the hydrogen on the hydroxyl is very active, but also the ortho-position and para-position of a benzene ring become active under the action of the hydroxyl, so long-carbon chain alkyl can be introduced by alkylation of the phenolic hydroxyl; alkyl groups may also be introduced by the Mannich reaction; the alkyl group may also be introduced indirectly by introducing an alkylphenol by a condensation reaction.
Their chemical reaction is as follows:
(1) an alkylation method:
(2) mannich reaction method:
(3) condensation reaction method:
Figure C9910757900044
the modified lignosulfonate prepared by the three methods can greatly improve the surface activity of the lignosulfonate. But the alkylation method (1) has long route and high cost, the Mannich reaction method (2) has higher price of aliphatic amine and still higher cost, and the condensation reaction method (3) has better industrial prospect, and after production, the sale price of the product can be controlled within the specified price.
Based on the above inventive idea, the following technical scheme is proposed:
the invention prepares the lignosulfonate surfactant by the following method, which comprises the following steps:
a) taking lignin, phenol and formaldehyde as raw materials;
b) in the condensation step, the three raw materials are subjected to condensation reaction at the temperature of 100-150 ℃ for 2-5 hours;
c) continuously adding sodium sulfite to sulfonate the condensation product at the temperature of 140 ℃ and 155 ℃ for 1-4 hours;
d) drying the sulfonation product, filtering, and drying at 70-90 deg.C to obtain the final product.
In the above production method, the phenol in the step a) is C6-C10The alkylphenol of (1).
In the above production method, the phenol in the step a) is preferably nonylphenol.
In the above preparation method, the condensation reaction temperature in step b) is 120-.
In the above production method, the condensation reaction time in the step b) is preferably controlled to 3 hours.
In the above preparation method, the sulfonation temperature in step c) is 150 ℃, the sodium sulfite concentration is 4% (wt), and the molar ratio of lignin to sodium sulfite is 1.05: 1.
The technology of the invention further comprises the application of the lignosulfonate surfactant as a compound agent in tertiary oil recovery.
Drawings
The invention comprises the following figures:
FIG. 1 is a block diagram of a process for preparing a lignosulfonate in accordance with the present invention;
FIG. 2 is a interfacial tension curve for the formulation of lignosulfonate with alkylbenzenesulfonate in accordance with the present invention.
The technical contents of the present invention and the significant technical effects brought by the technical contents will be described in detail below with reference to the accompanying drawings and specific embodiments.
Detailed Description
Example 1
According to the scheme shown in FIG. 1, 150 kg of sodium sulfite was added to a plurality of water, and stirred well until it was completely dissolved, and then 700 kg of lignin was gradually added thereto and stirred for 1 hour. 140 kg of 37% formaldehyde was slowly added dropwise thereto, and the mixture was stirred for 10 minutes. Thereafter, 70 kg of nonylphenol was added and stirred for 10 minutes. The mixed reaction solution was introduced into a 100L autoclave, heated in an oil bath, and reacted for 3 hours at a temperature of 130 ℃. After that, filtration and drying at 80 ℃ for 6 hours gave about 1 ton of the product lignosulfonate.
Example 2
The lignosulfonate was prepared in the same manner as in example 1, except that the reaction temperature of the raw materials in the autoclave was controlled at 110 ℃ for 5 hours.
Example 3
The lignosulfonate was prepared in the same manner as in example 1, except that the reaction temperature of the raw materials in the autoclave was controlled at 150 ℃ for 2 hours.
Example 4
The procedure of example 1 was repeated, except that the amount of sodium sulfite was 150 kg, the amount of lignin was 700 kg, 686 kg of nonylphenol and 140 kg of formaldehyde were added, to obtain lignosulfonate.
Example 5
The procedure of example 1 was repeated, except that octylphenol was used instead of the phenol compound in an amount of 655 kg, to obtain lignosulfonate in the same manner as in example 1.
Example 6
The procedure of example 1 was repeated, except that heptol was used in an amount of 610 kg instead of the phenol-based substance, to obtain lignosulfonate in the same manner as in example 1.
Example 7
The same procedure as in example 1 was repeated except that the lignin used was wood pulp alkali lignin, and the waste liquid from the paper mill was treated and then charged into the reactor, to obtain lignosulfonate in the same manner as in example 1.
The product of the above example, calculated, costs about 0.3 ten thousand yuan/ton. The product is compounded with other active agents to form 10-3The ultra-low interfacial tension (the experimental apparatus is a Model-500 type rotary drop interfacial tension apparatus produced by the American university of Texas) with the mN/m order of magnitude is used for an oil displacement test after being compounded, can achieve higher recovery ratio and meet the application requirement of the invention.
Example 8
Application of lignosulfonate as compounding agent for tertiary oil recovery
The lignosulfonate (WNS) produced in the above example and alkylbenzene sulfonate (ORS) were compounded in a ratio of 3: 1, and the fixed NaOH concentration in the system was 1.2 wt%. FIG. 2 shows that at 0.6 wt% active agent concentration, the system can form 10 with Daqing crude oil-3-10-4Ultra-low interfacial tension of the order of mN/m. Meanwhile, the interfacial tension of the WNS: ORS-3: 1 compound system can be seen from figure 2The force effect is significantly better than that of the individual ORS active agent system, which suggests that WNS products and ORS have better synergistic effect.
The product of the invention is subjected to an indoor natural core oil displacement experiment, the method is to perform an indoor oil displacement experiment of a lignosulfonate composite system on Daqing natural cores with the diameter of 2.5cm multiplied by 10cm, and the experimental result is shown in table 1. It can be seen from table 1 that the oil displacement efficiency is improved by more than 15% (OOIP) compared with water flooding, wherein the product oil displacement experimental result of the WNS and ORS composite system of example 7 is improved by 20.00% (OOIP) compared with water flooding, which indicates that the two active agents have higher synergistic effect and the composite system has better compatibility with Daqing oil water.
TABLE 1 indoor oil displacement test results
Active agent Total concentration of (wt% commercial product) Ratio of NaOH Concentration of (wt%) Polymer and method of making same Concentration of (ppm) Follow-up slug Concentration of Polymer (ppm) Specific water flooding lifter High recovery ratio (%OOIP)
Example 1 0.6 WNS∶ORS=3∶1 1.2 1200 800 16.27
Example 4 0.8 WNS∶ORS=3∶1 1.2 1200 800 18.32
Example 5 0.6 WNS∶ORS=3∶1 1.2 1800 800 18.90
Example 7 0.8 WNS∶ORS=3∶1 1.2 1800 800 20.00
According to the invention, although the single industrial lignosulfonate can not form ultra-low interfacial tension with Daqing crude oil, the lignosulfonate can generate better synergistic effect with a plurality of active agents, particularly with alkylbenzene sulfonate surfactants, and can form 10 with the Daqing crude oil within a wider range of the active agents, alkali and mineralization degree-3The ultra-low interfacial tension of mN/m order of magnitude, the indoor oil displacement experimental result shows that the oil displacement efficiency is improved by 15 percent OOIP compared with water displacement, and the oil displacement efficiency is 30 to 60 percent saved when being the same as the oil displacement efficiency of singly using ORS-41. If the cost is the same, the recovery ratio can be improved by 3-5 percent (OOIP).

Claims (7)

1. A lignosulfonate surfactant having a molecular weight of 380-500 prepared by a method comprising the steps of;
a) taking lignin, phenol and formaldehyde as raw materials;
b) in the condensation step, the three raw materials are subjected to condensation reaction at the temperature of 100-150 ℃ for 2-5 hours;
c) continuously adding sodium sulfite to sulfonate the condensation product at the temperature of 140 ℃ and 155 ℃ for 1-4 hours;
d) drying the sulfonation product, filtering, and drying at 70-90 deg.C to obtain the final product.
2. A lignosulfonate surfactant having a molecular weight of 380-500 prepared by a method comprising the steps of;
a) taking lignin, phenol and formaldehyde as raw materials;
b) in the condensation step, the three raw materials are subjected to condensation reaction at the temperature of 100-150 ℃ for 2-5 hours;
c) continuously adding sodium sulfite to sulfonate the condensation product at the temperature of 140 ℃ and 155 ℃ for 1-4 hours;
d) drying the sulfonation product, filtering, and drying at 70-90 deg.C to obtain the final product.
3. The process according to claim 2, wherein the phenol in step a of the preparation process is C6-C10The alkylphenol of (1).
4. The process according to claim 2, wherein the phenol in step a of the preparation process is nonylphenol.
5. The method as set forth in claim 2, wherein the condensation reaction temperature in step b of the preparation method is 120 ℃ to 130 ℃ and the reaction time is controlled to 3 hours.
6. The process according to claim 2, wherein in step c of the preparation process the sulfonation temperature is 150 ℃, the sodium sulfite concentration is 4% (wt) and the molar ratio is 1.05: 1.
7. Use of the lignosulfonate surfactant of claim 1 as a combination in enhanced oil recovery.
CNB99107579XA 1999-05-27 1999-05-27 Lignin sulfonate surfactant for oil field, its preparation process and use in tertiary oil recovery Expired - Lifetime CN1133486C (en)

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CN1298805C (en) * 2004-02-25 2007-02-07 石油大学(华东) Active collosol deep adjusting driving agnet
CN101147480B (en) * 2007-09-13 2010-08-11 华南理工大学 Modified lignosulfonate pesticide dispersing agent and its preparation method
CN101628884B (en) * 2009-07-01 2012-11-28 大庆高新区华龙祥化工有限公司 Preparation method of ampholytic surfactant and application thereof in tertiary oil recovery
CN103013459B (en) * 2011-09-28 2015-10-21 中国石油化工股份有限公司 A kind of super-high density drilling fluid dispersion agent, preparation method and application
CN102580610B (en) * 2012-01-09 2013-10-23 中科院广州化学有限公司 Lignosulfonate alkylation modified surfactant and preparation method and application thereof
CN109294547B (en) * 2018-10-23 2020-11-20 天津大港油田滨港集团博弘石油化工有限公司 Anionic and nonionic amphoteric surfactant for oil displacement and preparation method thereof

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