CN104448135B - Preparing method for heat resistance and salt tolerance polyacrylamide used in oil field - Google Patents
Preparing method for heat resistance and salt tolerance polyacrylamide used in oil field Download PDFInfo
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Abstract
The invention provides a preparing method for heat resistance and salt tolerance polyacrylamide used in an oil field. The preparing method comprises the following steps that acrylamide, 2- acrylamide-2-methyl sodium, sodium acrylate, aiding solvent and deionized water are mixed to be dissolved fully and uniformly, and alkali is used for adjusting a pH value to obtain a homopolymerisation solution; the homopolymerisation solution is pumped into a polymerizing pot after being cooled, 2,2'-azobis-(2-methylbutyronitrile) is added, nitrogen is introduced, chain extender is added at first, then solutions prepared by complexing agents, oxidizing agents, reducing agents and auxiliary reducing agents are added sequentially, after all the solutions are added, nitrogen continues to be introduced, the polymerization reaction is carried out, heat is preserved, and the aging reaction is carried out to obtain a polyacrylamide rubber block; the rubber block is taken out, cutting, pelleting, drying, smashing and screening are carried out on the rubber block to obtain high-hydrolysis-degree polyacrylamide. The polyacrylamide obtained through the method has the advantages of stable quality, high viscosity, heat resistance, salt tolerance, high dissolving speed and good solubility, the product energy consumption is low, and in the high-temperature and high-salinity environment, the viscosity is degraded slowly.
Description
Technical field
The present invention relates to a kind of oil field temperature-tolerant anti-salt polyacrylamide preparation method, category water soluble polymer synthesis neck
Domain.
Background technology
Polyacrylamide suffers from widely using in many fields, especially big in field of oilfield exploitation demand.With
The development of oilfield exploitation, most of oil field enters tertiary phase.In the three polyacrylamide characteristics for adopting stage application
Require：High viscosity, viscosity degradation rate is low under high temperature, high salinity, can long-time under the conditions of high temperature, the bottom of high salinity
Keep high-viscosity characteristic.The oil field temperature-resistant and anti-salt type polyacrylamide major part that currently there are is by changing polymerization work
Skill is rear hydrolytic polymerization skill, and increases hydrolysis machine to carry out secondary hydrolysis to improve its molecular weight, makes to reach more than 30,000,000
Molecular weight is guaranteeing that it, with the degraded of molecular weight, can still keep certain viscosity under the geological conditions of high temperature and high salt.Separately
There is the temperature-resistant anti-salt unit that portioned product adds 5% or so carrying sulfonic acid group in rear hydrolysation process to be polymerized outward,
Because sulfonic acid group has inhibition to polymerisation, through secondary hydrolytic process, its molecular weight is not still too high, and major part exists
Between 1800 ten thousand to 2,500 ten thousand.And because carrying out secondary hydrolysis, its dissolubility is poor, dissolution time is longer, it is more difficult to which meeting oil field makes
With.
The content of the invention
It is an object of the invention to provide a kind of oil field temperature-tolerant anti-salt polyacrylamide preparation method, is prepared by the method
Product quality stablize, viscosity is high, temperature-resistant anti-salt, in the environment of high temperature and high salinity, and viscosity degraded is slow, and dissolution velocity
Hurry up, dissolubility it is good, solve the difficult point during oil field temperature-resistant and anti-salt type polyacrylamide use in the market.
For achieving the above object, the present invention provide a kind of oil field temperature-tolerant anti-salt polyacrylamide preparation method include with
Lower step：
（1）, by weight percentage by acrylamide 14-16%, 2- acrylamide-2-methyl propane sulfonic sodium 13-15%, propylene
Sour sodium 0.55-1.45%, cosolvent 0.15-0.3%, deionized water 35-70% be sufficiently mixed stirring to CL it is uniform after, use alkali
PH value is adjusted to 6.5-7.5, transparent or semitransparent equal poly solution is obtained；
（2）, equal poly solution circulating cooling pumped in polymeric kettle to after 1-3 DEG C, addition is with homopolymerization solution quality ratio
The AMBN of 300-400ppm, after being passed through high pure nitrogen 30min, is initially charged chain extender solution, then sequentially adds
The concentration being configured to by complexing agent, oxidant, reducing agent, assistant reducing agent respectively is 5% solution, chain extender, complexing agent,
Oxidant, reducing agent, assistant reducing agent and the mass ratio of equal poly solution be respectively 700～800ppm, 50～65ppm, 25～
28ppm, 25～28ppm, 5～6ppm, keep being passed through high pure nitrogen in each solution adition process, and per two kinds of solution interval is added
For 10 minutes, continue to be passed through stopping after high pure nitrogen 5min after all adding, polymerization temperature is controlled at 3～5 DEG C, polymerisation
After 2～4 hours, then it is incubated 80～90 DEG C, aging reaction 4～6 hours obtains transparent resilient polyacrylamide blob of viscose；
（3）, take out blob of viscose, it is cut, granulated, be dried, crushed, sieved, obtain high degree of hydrolysis polyacrylamide.
In such scheme, acrylamide, 2- acrylamide-2-methyl propane sulfonic sodium, PAA weight ratio are folding
Weight ratio after dry.
In such scheme step（1）In, PAA is present as a solution, the preparation condition of sodium acrylate solution
For：(1), acrylic acid and NaOH are taken, and acrylic acid is 1.8 with the mass ratio of NaOH:1；(2), at 10 DEG C -30 DEG C, by hydrogen
Sodium oxide molybdena is configured to 30% sodium hydroxide solution, and sodium hydroxide solution is slowly added in acrylic acid.
In such scheme step（1）In, 2- acrylamide-2-methyl propane sulfonic sodium is present as a solution, 2- propylene
The preparation condition of acid amides -2- methyl propane sulfonic acid sodium solutions is：(1), 2- acrylamide-2-methyl propane sulfonics and NaOH, 2- are taken
Acrylamide-2-methyl propane sulfonic is 5.7 with the mass ratio of NaOH:1；(2), at 10 DEG C -30 DEG C, NaOH is prepared
Into 30% sodium hydroxide solution, 2- acrylamide-2-methyl propane sulfonics are slowly added in sodium hydroxide solution.
In such scheme, cosolvent is thiocarbamide or dimethylformamide or sodium salicylate.
In such scheme, chain extender solution be by mass ratio be 2.8～2.9:2.0～2.1:7:2.0～2.3:1:
45.5～45.8 ABVN, 3- methylamino propionitrile, 4,4'- azos double (cyanopentanoic acids), acetone, NaOH and pure
The homogeneous phase solution that water is formulated.
In such scheme, complexing agent is diethylene triamine pentamethylene phosphonic salt or sodium gluconate or ethylenediamine tetra-acetic acid
Salt, reducing agent is sodium sulfite, and oxidant is sodium peroxydisulfate, and assistant reducing agent is ferrous sulfate.
In such scheme, the alkali of pH value is adjusted from NaOH or sodium carbonate.
The present invention is the characteristics of prepare temperature-tolerant anti-salt polyacrylamide technique using terpolymerization：
（1）Because acrylamide, PAA, 2- acrylamide-2-methyl propane sulfonic sodium monomers add together in dispensing
Enter, adjust solution ph to 6.5-7.5, acrylamide hardly occurs hydrolysis in this medium, therefore, it is easier to accurately
The relatively Lower degrees of hydrolysis polyacrylamide product of prepared superior solubility.
（2）Simple process, because can solve with normal front hydrolysis process mixed production, equipment investment and low production cost
Afterwards hydrolysis device invests big, high energy consumption point really, and the degree of hydrolysis of product is accurately uniform.
（3）Redox initiation system can at low temperature cause polymerization, with reference to the chain extender of independent research, can make reaction
Process is steady, obtains polyacrylamide and has following characteristic：Narrow molecular weight distribution, molecular weight 1800～23,000,000 are glued for 30 days
Degree retention rate >=85%, specific filtration resistance≤1.2, screen factor >=25, the molten thing ＜ 0.1% in water portion, degree of hydrolysis≤25%；It is common with existing
Type high molecular weight polyacrylamide is compared, with thermo-salt resistance it is good, viscosity retention ratio is high, the characteristic of viscosity retention time length,
There is outstanding dissolubility and instant capacity.
Specific embodiment
The present invention is further illustrated below in conjunction with the embodiment of several preparation oil fields temperature-tolerant anti-salt polyacrylamide.
Embodiment 1：
（1）In 13m3Volume is allotted in the material-compound tank of volume for 11 m3Solution, wherein the 1.63T of quality containing acrylamide,
The pH value of the 155kg of quality containing PAA is 6.5（Concentration is 38～40%）Solution, thiocarbamide the 16kg, -2- of acrylamide containing 2-
The pH value of methyl propane sulfonic acid sodium quality 1.5T is 6.5 solution（Concentration is 38～40%）, deionized water moisturizing to 11m will
Above-mentioned raw materials are sufficiently mixed, mechanical agitation to solution is clarified, and pH value are adjusted to 7.1 with sodium carbonate, obtain without solid insoluble
Equal poly solution；According to mass ratio, ABVN：3- methylamino propionitrile：4,4'- azos are double (cyanopentanoic acid)：Acetone：Hydrogen-oxygen
Change sodium：Pure water=2.8：2.1:7:2.2:2:45.7 configuration 100kg, the chain extender solution that pH value is 7.5.
（2）By obtained homopolymerization liquid circulating cooling to after 1-1.5 DEG C, in pumping into polymeric kettle, add the azo two of 3.75kg different
Valeronitrile, after being passed through high pure nitrogen 30min, is first uniformly added into the chain extender solution that 8.25kg is configured, and then sequentially adds dense
Degree is 5% following solution：Edetate solution, edetate content 0.605kg, potassium persulfate solution,
Potassium peroxydisulfate content 0.28kg, sodium sulfite solution, sodium sulfite content 0.28kg, copperas solution, ferrous sulfate content
0.065kg, the above is added at intervals of 10 minutes per two kinds of solution, keeps being passed through nitrogen in adition process, is continued after all adding
It is passed through after high pure nitrogen 5min and stops nitrogen charging, at 4 DEG C, cause polymerization, react 2.8h, at 80 DEG C, then is incubated aging reaction
7h, obtains transparent resilient blob of viscose.
（3）Blob of viscose is taken out, cut, granulated, dry, crushing, screening are obtained：20～80 mesh, molecular weight 24,600,000, admittedly contain
Amount 90.8%, degree of hydrolysis 23.5%, 60～80min of dissolution velocity, 75 DEG C, apparent viscosity 24.6mpa.s, lucifuge under 20,000 salinities
Viscosity retention ratio is 89% after standing 30 days, the white powder temperature-resistant and anti-salt type polyacrylamide of specific filtration resistance≤1.2.
Embodiment 2：
（1）In 13m3Volume is allotted in the material-compound tank of volume for 11 m3Solution, wherein the 1.57T of quality containing acrylamide,
The pH value of the 60kg of quality containing PAA is 6.5 solution, dimethylformamide 16kg, acrylamide-2-methyl propane sulfonic containing 2-
The pH value of sodium quality 1.66T is 6.5 solution, deionized water moisturizing to 11m, above-mentioned raw materials is sufficiently mixed, mechanical agitation
To solution clarification, pH value is adjusted to 7.1 with NaOH, obtained without the equal poly solution of solid insoluble；According to mass ratio, azo
Two different heptonitriles：3- methylamino propionitrile：4,4'- azos are double (cyanopentanoic acid)：Acetone：NaOH：Pure water=2.9：2.1:7:2.2:
1:45.7 configuration 100kg, the chain extender solution that pH value is 7.5.
（2）By obtained homopolymerization liquid circulating cooling to after 1-1.5 DEG C, in pumping into polymeric kettle, the azo diisoamyl of 4kg is added
Nitrile, after being passed through high pure nitrogen 30min, is first uniformly added into the chain extender that 8.8kg is configured, and then sequentially adds concentration and is 5%
Following solution：Sodium gluconate, gluconic acid sodium content 0.55kg, sodium peroxydisulfate solution, sodium peroxydisulfate content 0.3kg is sub-
Metabisulfite solution, sodium sulfite content 0.3kg, copperas solution, ferrous sulfate content 0.065kg, the above is per two kinds of solution
Add at intervals of 10 minutes, keep being passed through nitrogen in adition process, continue to be passed through stopping after high pure nitrogen 5min after all adding
Nitrogen charging, at 3.6 DEG C, causes polymerization, reacts 3h, at 80 DEG C, then is incubated aging reaction 7h, obtains transparent resilient glue
Block.
（3）Blob of viscose is taken out, cut, granulated, dry, crushing, screening are obtained：20～80 mesh, molecular weight 27,100,000, admittedly contain
Amount 90.6%, degree of hydrolysis 24.9%, 60～80min of dissolution velocity, 75 DEG C, apparent viscosity 27.2mpa.s, lucifuge under 20,000 salinities
Viscosity retention ratio is 88.7% after standing 30 days, the white powder temperature-resistant and anti-salt type polyacrylamide of specific filtration resistance≤1.2.
Embodiment 3：
（1）In 13m3Volume is allotted in the material-compound tank of volume for 11 m3Solution, wherein the 1.73T of quality containing acrylamide,
The pH value of the 60kg of quality containing PAA is 6.5 solution, sodium salicylate 16kg, the sodium of acrylamide-2-methyl propane sulfonic containing 2-
The pH value of quality 1.49T is 6.5 solution, deionized water moisturizing to 11m, above-mentioned raw materials are sufficiently mixed, mechanical agitation extremely
Solution is clarified, and pH value is adjusted to 7.1 with sodium carbonate, is obtained without the equal poly solution of solid insoluble；According to mass ratio, azo two is different
Heptonitrile：3- methylamino propionitrile：4,4'- azos are double (cyanopentanoic acid)：Acetone：NaOH：Pure water=2.9：2.1:7:2.3:1:
45.6 configuration 100kg, the chain extender solution that pH value is 7.5.
（2）By obtained homopolymerization liquid circulating cooling to after 1-1.5 DEG C, in pumping into polymeric kettle, the azo diisoamyl of 4.2kg is added
Nitrile, after being passed through high pure nitrogen 30min, is first uniformly added into the chain extender solution that 7.7kg is configured, and then sequentially adds concentration equal
For 5% following solution：Diethylene triamine pentamethylene phosphonic salt, diethylene triamine pentamethylene phosphonic salt content 0.605kg, over cure
Sour potassium solution, potassium peroxydisulfate content 0.305kg, sodium sulfite solution, sodium sulfite content 0.305kg, copperas solution, sulphur
Sour ferrous content 0.065kg, the above is added at intervals of 10 minutes per two kinds of solution, keeps being passed through nitrogen in adition process, all
Continue to be passed through after high pure nitrogen 5min after addition and stop nitrogen charging, at 4.1 DEG C, cause polymerization, react 2.6h, at 80 DEG C, then
Insulation aging reaction 7h, obtains transparent resilient blob of viscose.
（3）Blob of viscose is taken out, cut, granulated, dry, crushing, screening are obtained：20～80 mesh, molecular weight 22,000,000, admittedly contain
Amount 89.8%, degree of hydrolysis 21.1%, 60～80min of dissolution velocity, 75 DEG C, apparent viscosity 24.4mpa.s, lucifuge under 20,000 salinities
Viscosity retention ratio is 89.7% after standing 30 days, the white powder temperature-resistant and anti-salt type polyacrylamide of specific filtration resistance≤1.2.
Claims (1)
1. a kind of oil field temperature-tolerant anti-salt polyacrylamide preparation method, it is characterised in that comprise the following steps：
（1）, by weight percentage by acrylamide 14-16%, 2- acrylamide-2-methyl propane sulfonic sodium 13-15%, PAA
0.55-1.45%, cosolvent 0.15-0.3%, deionized water 35-70% be sufficiently mixed stirring to CL it is uniform after, with alkali by pH
Value is adjusted to 6.5-7.5, obtains transparent or semitransparent equal poly solution；
（2）, equal poly solution circulating cooling pumped in polymeric kettle to after 1-3 DEG C, it is 300- to add with homopolymerization solution quality ratio
The AMBN of 400ppm, after being passed through high pure nitrogen 30min, is initially charged chain extender solution, then sequentially adds difference
The concentration being configured to by complexing agent, oxidant, reducing agent, assistant reducing agent is 5% solution, chain extender, complexing agent, oxidation
Agent, reducing agent, assistant reducing agent and the mass ratio of equal poly solution be respectively 700～800ppm, 50～65ppm, 25～28ppm,
25～28ppm, 5～6ppm, keep being passed through high pure nitrogen in each solution adition process, add at intervals of 10 points per two kinds of solution
Clock, continues to be passed through stopping after high pure nitrogen 5min after all adding, and polymerization temperature is controlled at 3～5 DEG C, and polymerisation 2～4 is little
Shi Hou, then it is incubated 80～90 DEG C, aging reaction 4～6 hours obtains transparent resilient polyacrylamide blob of viscose；
（3）, take out blob of viscose, it is cut, granulated, be dried, crushed, sieved, obtain high degree of hydrolysis polyacrylamide；
Described chain extender solution be by mass ratio be 2.8～2.9:2.0～2.1:7:2.0～2.3:1:45.5～45.8
What ABVN, 3- methylamino propionitrile, 4,4'- azos double (cyanopentanoic acids), acetone, NaOH and pure water were formulated
Homogeneous phase solution.
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| CN105399897B (en) * | 2015-12-30 | 2017-08-25 | 中国石油化工股份有限公司 | Temperature-tolerant anti-salt polyacrylamide is birdsed of the same feather flock together compound and preparation method thereof |
| CN107759730B (en) * | 2017-08-17 | 2020-10-09 | 东营聚星石油科技有限公司 | Preparation method of biomass modified polyacrylamide for oil displacement and recovery |
| CN109762101A (en) * | 2018-12-04 | 2019-05-17 | 山东水衡化工有限责任公司 | A kind of preparation method of superelevation salt-resistant polymer |
| CN109722232A (en) * | 2018-12-22 | 2019-05-07 | 河南正佳能源环保股份有限公司 | A kind of instant viscoplasticity oil displacement system of heterogeneous seawater for offshore oilfield, preparation method and application |
| CN113429512B (en) * | 2021-06-02 | 2022-08-02 | 宁波锋成先进能源材料研究院有限公司 | Application of water-soluble polymer as curing agent in cement-based material |
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| CN102649828A (en) * | 2012-05-25 | 2012-08-29 | 安徽巨成精细化工有限公司 | Preparation method of ultrahigh-hydrolysis-degree polyacrylamide |
| CN102977877A (en) * | 2012-12-04 | 2013-03-20 | 西南石油大学 | Drag reducer for shale gas fracture and preparation method of drag reducer |
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| CN102649828A (en) * | 2012-05-25 | 2012-08-29 | 安徽巨成精细化工有限公司 | Preparation method of ultrahigh-hydrolysis-degree polyacrylamide |
| CN102977877A (en) * | 2012-12-04 | 2013-03-20 | 西南石油大学 | Drag reducer for shale gas fracture and preparation method of drag reducer |
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