CN106867493A

CN106867493A - A kind of Powdey cross-linked dose of synthesis of novel solid and the experimental technique for purifying

Info

Publication number: CN106867493A
Application number: CN201710119218.2A
Authority: CN
Inventors: 吴景春; 赵阳; 石芳; 夏鹏辉; 吴松艳; 李玉波
Original assignee: Northeast Petroleum University
Current assignee: Northeast Petroleum University
Priority date: 2017-03-02
Filing date: 2017-03-02
Publication date: 2017-06-20

Abstract

The present invention relates to a kind of synthesis of crosslinking agent and the experimental technique for purifying, and in particular to the experimental technique of a kind of Powdey cross-linked dose of synthesis of novel solid and purification.Take 1 mole of CrCl₃Powder and 2.5~4 moles of NaAc, by CrCl₃In dissolving in the distilled water of 45~60ml with NaAc mixing, reaction temperature is 55~85 DEG C, and pH value is 7.5~9.5, and mixing speed is 280~460r/min, and the time is 5~8h, after the reaction time is more than half, 1~5% ethylene glycol is added to system；Reaction extracts solid after terminating, and ultra-pure water is added after the moisture in the aqueous solution is evaporated, and is filtered again and be concentrated by evaporation, and solid powder is purified in triplicate；Change CrCl₃With the mol ratio of NaAc, respectively repeatedly aforesaid operations step, will extract solid powder carries out cross-linking reaction with HPAM respectively, and detect its whether plastic, the optimal product target powder shape crosslinking agent of performance.

Description

A kind of Powdey cross-linked dose of synthesis of novel solid and the experimental technique for purifying

Technical field：

The present invention relates to a kind of synthesis of crosslinking agent and the experimental technique for purifying, and in particular to a kind of Powdey cross-linked dose of novel solid Synthesis and the experimental technique for purifying.

Background technology：

Current oil field development majority is a large amount of to inject due to the anisotropism on stratum in the waterflooding extraction later stage based on waterflooding extraction Water forms low effective circulation passage after entering stratum, causes great amount of injection water to be lost in and wastes, it is difficult to plays expected oil displacement efficiency.For Reduction low effective circulation passage, it is necessary to effectively blocked to high permeability zone, so as to improve the swept volume of injection water and involve Efficiency.Closure high-permeability reservoir is often preferably and smaller to formation damage with Weak Gels effect in plugging agent, and prepares convenient.Wherein With Cr³⁺For crosslinking central ion cross-linked polyacrylamide forms polynuclear hydroxy bridge complex ion Weak Gels.And existing crosslinking agent is generally Cr³⁺The aqueous solution, its production, transport, storage, cross-linking system prepare and live injection in terms of have inconvenience.Relative to normal Rule Cr³⁺Aqueous solution type crosslinking agent, solid powder type crosslinking agent have conveniently transport, be easy to store, being easy to cross-linking system to prepare, The advantage such as scene injection and delayed cross-linking.

The content of the invention：

The present invention makes up and improves above-mentioned the deficiencies in the prior art part, relative to conventional Cr³⁺Aqueous solution type crosslinking agent, Solid powder type crosslinking agent have conveniently transport, be easy to store, being easy to cross-linking system to prepare, scene injection and delayed cross-linking etc. it is excellent Point.

The technical solution adopted by the present invention is：A kind of Powdey cross-linked dose of synthesis of novel solid and the experimental technique for purifying, It is characterized in that：The experimental technique is:

The first step:Take 1 mole of CrCl₃Solid powder and 2.5~4 moles of NaAc, by CrCl₃With NaAc mixing dissolve in 45~ In the distilled water of 60ml, and above-mentioned solution is placed in heating synthetic reaction is carried out in there-necked flask, reaction temperature is 55~85 DEG C, PH value is 7.5~9.5, and mixing speed is 280~460r/min, and total reaction time is 5~8h, when the reaction time of above-mentioned reaction After reaching the half of total reaction time, to the ethylene glycol that 1~5% is added in the system of above-mentioned there-necked flask, the addition of the ethylene glycol It is the 1~5% of there-necked flask liquor capacity to measure, and persistently enters the regulation of trip temperature, pH value and mixing speed；

Second step：The aqueous solution is obtained after the synthesising reacting time of the first step reaches total reaction time, by filtering and evaporating dense The mode of contracting extracts the solid in the above-mentioned aqueous solution, in extraction process, is added after the moisture in the aqueous solution is evaporated ultrapure Water, and filtered again and be concentrated by evaporation, repeat to filter and be concentrated by evaporation three times to purify solid powder；

3rd step：Change CrCl₃With the mol ratio of NaAc, the repeatedly operating procedure of the first step and second step, obtains different respectively CrCl₃With the solid powder under NaAc molar ratios, it is standby；

4th step：Solid powder in 3rd step is carried out into cross-linking reaction with HPAM respectively, in each crosslinking inverse process, every 24 Hour test its viscosity, detect its whether plastic, viscosity is considered as plastic when reaching 1400mPa s, goes forward side by side line number according to statistics and number According to analysis, if plastic, the optimal solid powdery crosslinking agent of performance is Powdey cross-linked dose of novel solid in the glue, that is, obtain CrCl₃With the optimization mol ratio of NaAc, the mol ratio is the formula for preferably producing Powdey cross-linked dose of novel solid.

By changing CrCl in the 3rd described step₃The solid powder under the conditions of different mol ratio is obtained with the mol ratio of NaAc End, the solid state powder is no less than five kinds.

Beneficial effects of the present invention：Technological design is rationally, simple to operate, and implementation is strong, and experiment effect is obvious, low cost It is honest and clean, can effectively instruct actual production, it is easy to promote on a large scale and use.The method passes through chemical Organic Experiment, success Synthesis has purified a kind of solid powder type crosslinking agent for being different from conventional soln type crosslinking agent.The solid powder type crosslinking agent has It is easy to store, transports and the advantages of the injection of scene.Shown by laboratory experiment result, the solid powder type crosslinking agent can be fine Cross-linking reaction is carried out with HPAM, the gelling strength required for reaching Oil Field application, gelation time is controllable, economical and practical, Can extensive use and popularization in the field polymers displacement of reservoir oil.

Brief description of the drawings：

Fig. 1 is C1, C2, C3, C4 and C5 powder and HPAM reaction friendship plastic variation diagrams in embodiment.

Specific embodiment：

Step one：It is 1 and 2,1 and 2.5,1 and 3,1 and 3.5 and 1 and 4 mole of CrCl to take mole respectively₃It is mixed with NaAc powder Compound A1, A2, A3, A4 and A5, mixture A1, A2, A3, A4 and A5 are respectively put into there-necked flask, and add 45~60ml Distilled water, reacted respectively, reaction temperature adjustable range be 60~75 DEG C, pH value adjustable range be 7.5~9.5, stirring Speed adjustable range be 280~460r/min, total reaction time be 7 hours, when reacted between reach 3.5 hours after, respectively to 3% ethylene glycol is added in the system of there-necked flask, the addition of the ethylene glycol is 3% of surplus solution volume in there-necked flask, Persistently enter the regulation of trip temperature, pH value and mixing speed.Above-mentioned reaction respectively obtained after terminating five groups of purple aqueous solution B1, B2, B3, B4 and B5, the color of B1 to the B5 aqueous solution are gradually deepened by shallow, wherein there is solids of sedimentation to separate out.

Step 2：B1, B2, B3, B4 and B5 aqueous solution in step one is distinguished into continuous heating, is positioned over after moisture evaporation Low temperature environment is cooled down, the solid in extracting the above-mentioned aqueous solution by way of filtering and being concentrated by evaporation, in extraction process, when Moisture in the aqueous solution adds ultra-pure water after being evaporated, and is filtered again and be concentrated by evaporation, and repeats to filter and be concentrated by evaporation three It is secondary to purify solid powder, finally obtain solid powder C1, C2, C3, C4 and C5.

Step 3：Solid powder C1, C2, C3, C4 and C5 carry out mixed preparing cross-linking system with HPAM solution respectively, every In individual crosslinking inverse process, test its viscosity within every 24 hours, detect its whether plastic, viscosity is considered as plastic when reaching 1400mPa s, And viscosity ascendant trend substantially or is persistently kept above into adhesiveness, then plastic works well, the cross-linking reaction principle of its plastic For：

Complexing：

Hydrolysis：

Ol bridge is acted on：

Further hydrolysis and ol bridge effect：

The partially hydrolyzed polyacrylamide (PHPA) of the polynuclear hydroxy bridge complex ion crosslinking band-COO- of chromium（HPAM）Produced crosslinked is：

Above-mentioned experimental data such as table 1 below

Table 1：C1, C2, C3, C4 and C5 solid powder and HPAM reaction plastic tables of data

By the analysis to experimental data in Fig. 1 and Biao 1, it can be deduced that solid powder C1 and C5 fail to be crosslinked HPAM, and powder Although last C2 and C3 is so that HPAM is crosslinked, cross-linking effect is bad, and its viscosity number is relatively low, does not reach use requirement.From experiment number According to middle its reason of analysis, powder C1 and C5 unreacted is not complete, does not obtain target product, though and powder C2 and C3 obtain target Product, but purity wherein content is arrived use requirement in other words, researched and analysed by experimental data, powder C4 can make HPAM is crosslinked, and plastic is in order, and viscosity number is higher, disclosure satisfy that use requirement, so powder C4 is target product, Powdey cross-linked dose of novel solid i.e. to be prepared, it can be deduced that molfraction ratio is 1：3.5 CrCl₃It is preparation with NaAc The optimized proportion that Powdey cross-linked dose of novel solid, the molfraction is than to prepare and produce Powdey cross-linked dose of novel solid Formula.

Claims

1. the experimental technique of a kind of synthesis of Powdey cross-linked dose of novel solid and purification, it is characterised in that：The synthesis of the crosslinking agent It is with method of purification:

2. the experimental technique of a kind of synthesis of Powdey cross-linked dose of novel solid according to claim 1 and purification, its feature It is：By changing CrCl in the 3rd described step₃The solid powder under the conditions of different mol ratio is obtained with the mol ratio of NaAc, The solid state powder is no less than five kinds.