CN1117803C - Process for preparing high-Al aluminium citrate cross-linking agent - Google Patents
Process for preparing high-Al aluminium citrate cross-linking agent Download PDFInfo
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- CN1117803C CN1117803C CN 00135877 CN00135877A CN1117803C CN 1117803 C CN1117803 C CN 1117803C CN 00135877 CN00135877 CN 00135877 CN 00135877 A CN00135877 A CN 00135877A CN 1117803 C CN1117803 C CN 1117803C
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Abstract
The present invention provides a novel method for manufacturing a liquid or solid citric acid aluminum cross-linking agent of the polymer cross-linking technology used for increasing the collecting rate in the processes of secondary oil collection and tertiary oil collection in oil fields. The citric acid aluminum cross-linking agent manufactured by using the method does not contain sulfate radicals or nitrate ions. The citric acid aluminum cross-linking agent is the mixture mainly composed of aluminium ions, citric acid radicals and other inorganic salts brought in a manufacturing process. The molar ratio of the aluminium ions and the chlorine ions in the citric acid aluminum cross-linking agent manufactured according to the patent is not higher than 3. The present invention is suitable for preparing the polymer gelatin of intensified oil production.
Description
Technical field
The invention provides a kind of method of new manufacturing liquid or solid Tiorco 677 linking agent.Adopt the liquid or solid Tiorco 677 linking agent of manufacturing of the present invention to be applicable to the crosslinked polymer technology that improves recovery ratio in oil field secondary and the tertiary oil recovery process.
Background technology
Tiorco 677 linking agent and suitable polymer formation cross-linking polymer system are used for heterogeneous reservoir, can improve the unhomogeneity of permeability variation oil reservoir, increase the obstruction to height infiltration waterflooded area inner fluid.Make follow-up displacing fluid enter middle low permeability layer, further improve the sweep efficiency of oil reservoir, thereby play the purpose that improves ultimate recovery factor.
Tiorco 677 is as linking agent, and trivalent aluminium ion wherein is an active ingredient, and citric acid and its complexing delay it and polymkeric substance carries out crosslinked speed.Introduce according to United States Patent (USP)s in 1973 (US Pat.3,762,474), the Tiorco 677 that use first in the oil field is to be mixed by powdery hydrazine aluminum sulfate and Sodium Citrate, usp, Dihydrate Powder, and water is made into finite concentration and injects the stratum.The linking agent that makes thus has following shortcoming: (1) pH value is lower, to the oil field equipment seriously corroded; (2) sulfate radical can be strengthened some oil-field water fouling trend in the composition; (3) adopt this method, the complexing between trivalent aluminium ion and the citric acid is insufficient, and aluminum ion adsorbs in the immediate vicinity of wellbore easily, or forms gel in the immediate vicinity of wellbore.It is the method that raw material is made liquid Tiorco 677 linking agent with aluminum chloride and Tai-Ace S 150 that English Patent (BP 1,598,709) has been introduced a kind of, gained pH value of solution value≤4, and wherein the mol ratio of aluminium and citric acid is 5.2: 1, is not suitable for to improve oil recovery rate.To improve oil recovery rate desired 6.5 the time when the pH value of solution value is increased to, and the aluminum ion of complexing does not precipitate.The complete aluminum ion that allows of aluminum ion and citric acid complex: citric acid is 2.2: 1 to the maximum.United States Patent (USP) (US Pat.4,447,364) introduced the method that adopts the manufacturing of improving one's methods to be used to improve the oil recovery rate Tiorco 677, this method is a raw material with aluminum chloride and citric acid, ammoniacal liquor is pH value conditioning agent, make aluminium ion concentration 2.25～3%, pH value 5.5～7.5, aluminum ion: the linking agent product of citric acid=1.5: 1～2: 1.But, make troubles for transportation and storage because effective concentration is crossed low and freezing point is higher.It is the method that raw material is made the Tiorco 677 linking agent of aluminium ion concentration 3.0～3.5% with sodium aluminate and citric acid or Trisodium Citrate that United States Patent (USP) (US Pat 4,601,340) has been introduced another, the aluminium ion concentration 3.0% that patent is recommended.Patent (the US Pat.5 that U.S. Tiorco company in 1996 and 1997 delivers, 559,261 and US Pat.5,654,261) manufacture method and the purposes about the Tiorco 677 linking agent in the past being commented, is raw material with aluminium chlorohydroxide and citric acid, ammoniacal liquor is pH value conditioning agent, make aluminium ion concentration 3.1～5.1%, pH value 6.5～7.5, aluminum ion: citric acid≤2.2: 1 liquid cross-linker product or the powder-like product that obtains through super-dry.
By the linking agent that adopts above the whole bag of tricks to make is estimated, find that impurities in raw materials is very big to its gel-forming property influence, is necessary to study a kind of new Tiorco 677 manufacture method.
Summary of the invention
The object of the present invention is to provide a kind of preparation method who is applicable to the high-Al aluminium citrate cross-linking agent of oil field secondary and tertiary oil recovery process.
The present invention is achieved in that aluminum ion is provided by aluminum chloride (anhydrous or crystallization) and sodium aluminate respectively, and its preparation process is as follows:
1. citric acid and deionized water compound concentration are 50% aqueous citric acid solution;
2. under agitation slowly add aluminum chloride, 95～105 ℃ of reactions 2 hours that heat up then, the hydrogenchloride that displaces is water and sodium hydroxide solution absorption respectively;
3. under agitation add 50% sodium aluminate solution, control total aluminum ion,, stop heating, be cooled to 65～75 ℃ 105～110 ℃ of reactions 4 hours down than citric acid=1.5: 1～2.2: 1;
4. under agitation, add high alkali liquid, make PH=5.5～8.5;
5. remove by filter insolubles, obtain aluminium composition and be 3.5～5.5% liquid Tiorco 677 linking agent product;
6. through super-dry, crystallization, obtain aluminium composition greater than 10% solid citric acid aluminum crosslinker product.
The present invention also adopts following technical scheme:
The mol ratio that aluminum ions aluminum chloride and sodium aluminate are provided is 3: 1～1: 1.
The high alkali liquid that is added adopts 25～28% ammoniacal liquor.
Add high alkali liquid ammoniacal liquor, the amount of its ammoniacal liquor reaches PH=6.5～7.0 that make reaction system.
The Tiorco 677 linking agent that employing present method makes is sulfur-bearing acid group, nitrate ion not, and the Tiorco 677 linking agent mainly is by aluminum ion, citrate, and the mixture of other inorganic salt composition of bringing in the manufacturing processed.Mol ratio≤3 according to aluminum ion and chlorion in the Tiorco 677 linking agent of this patent manufacturing.Be applicable to the polymer gel of preparation intensified oil reduction.
Compare with the whole bag of tricks of making the Tiorco 677 linking agent in the past, the present invention has following characteristics:
1) adopts technology provided by the invention, can make the liquid Tiorco 677 linking agent product of aluminium composition more than 5.0%.
2) adopt in the Tiorco 677 linking agent product that the present invention makes not sulfur-bearing acid group, nitrate radical, inorganic salt content is lower than the product that adopts previous methods to obtain in the product.
3) adopt that iron ion content is lower than the product that adopts previous methods to obtain in the Tiorco 677 linking agent product that the present invention makes.
4) liquid product is through super-dry, can obtain aluminium composition greater than 10% solid phase prod, is convenient to the transportation of product and stores under severe environmental conditions.
Making the Tiorco 677 linking agent among the present invention may further comprise the steps:
1) citric acid and the deionized water of adding requirement are prepared certain density aqueous citric acid solution;
2) slowly add the Aluminum chloride anhydrous (or crystal aluminum chloride) that measures in above-mentioned solution, be warming up to 95～105 ℃ of reactions after adding more than two hours, the hydrogenchloride difference water and the aqueous sodium hydroxide solution that displace absorb;
3) in above-mentioned reaction solution, add the sodium aluminate solution that measures, control total aluminum ion: citric acid=1.5: 1～2.2., stop heating and be cooled to 65～75 ℃ more than four hours 105～110 ℃ of reactions then;
4) regulate above pH value of reactants between 5.5～8.5.Remove by filter insolubles then and obtain liquid Tiorco 677 linking agent product.
5) liquid product obtains solid citric acid aluminum crosslinker product through super-dry.
The pH value conditioning agent that uses in the pH value regulate process adopts the strong solution of molecular formula as the compound of MOH, and M is alkalimetal ion or ammonium ion in the formula.Aluminum ion is provided jointly by aluminum chloride and sodium aluminate two compounds among the present invention, and the mol ratio between the two is 2.0: 1～1: 1.The adding mode of citric acid adds in the first step of making the linking agent process with different in the past, utilizes the reaction between citric acid and aluminum chloride, displaces hydrogenchloride, reduces the inorganic salt content of the finished product.
Difference according to the concentration of each compound solution that disposes in the preparation process, and the mol ratio of aluminum chloride that adopts and sodium aluminate two compounds be 2.0: 1～1: 1 different, can obtain aluminium ion concentration is 3.5～5.5% (wt), pH value 6.5～7.5, aluminum ion: the liquid cross-linker product of citric acid≤2.2: 1.
Drying process can be selected general drying plant for use, but the present invention recommends to adopt rotary dryer to carry out drying.
Solid citric acid aluminum crosslinker product dissolves in water, also can be used for secure ph 6.5～7.5, and aluminium ion concentration is 1～3.5% (wt) liquid Tiorco 677 linking agent product.
The present invention passes through the research to the crosslinking reaction mechanism of Tiorco 677 linking agent and polymkeric substance, to activeconstituents in the Tiorco 677 linking agent, other minor component has more deep understanding to the influence of crosslinking reaction, has proposed new Tiorco 677 linking agent manufacturing process on this basis.With Tiorco 677 linking agent synthesis technique was different in the past, aluminum ion is provided by aluminum chloride (anhydrous or crystallization) and sodium aluminate respectively among the present invention; Citric acid add opportunity by after add to change at first and add, suitably improve temperature of reaction, strengthen the reaction of citric acid and aluminum chloride, displace hydrogenchloride as far as possible, reduce the consumption of neutralization reaction alkali, the inorganic salt content of reduction the finished product improves aluminum ions content.
The present invention includes and at first make dense Tiorco 677 cross-linking agent solution, liquid product obtains solid citric acid aluminum crosslinker product through super-dry then, and uses the solid phase prod preparation to be applicable to the polymer gel of intensified oil reduction.
The manufacturing of liquid Tiorco 677 linking agent may further comprise the steps:
1) citric acid and the deionized water of adding requirement, compound concentration is 50% aqueous citric acid solution;
2) keep under the good stirring state, the slow aluminum chloride (anhydrous or crystallization) that adds metering in above-mentioned solution was warming up to 95～105 ℃ of reactions more than two hours after adding, and the hydrogenchloride that displaces is water and aqueous sodium hydroxide solution absorption respectively;
3) keep under the good stirring state, in above-mentioned reaction solution, add 50% sodium aluminate solution of metering, control total aluminum ion: citric acid=1.5: 1～2.2: 1., stop heating and be cooled to 65～75 ℃ more than four hours 105～110 ℃ of reactions then;
4) keep under the good stirring state, add high alkali liquid and regulate above pH value of reactants between 5.5～8.5, be preferably in 6.5～7.0.High alkali liquid preferably uses 25～28% ammoniacal liquor.
5) remove by filter insolubles then and obtain aluminium composition 3.5～5.5% liquid Tiorco 677 linking agent products.
For the ease of storing under product long-distance transport and the severe environmental conditions, liquid Tiorco 677 linking agent can adopt some drying processes commonly used, carry out drying as spraying drying, drum drying, crystallization and some other suitable evaporation technology, obtain aluminium composition greater than 10% solid citric acid aluminum crosslinker product.
Liquid or solid Tiorco 677 linking agent product can with suitable polymkeric substance, be 5%～30% partially hydrolyzed polyacrylamide as degree of hydrolysis, in water, form cross-linked polymer solution or gel with suitable concentration, be used for the water blockoff or the transfer drive of oil reservoir.Liquid Tiorco 677 linking agent product can be directly or through dilution back and polymers soln again line mix, inject the stratum then.The solid linking agent can be made into certain density solution at the scene and use, and also can produce the special copolymer product in polymkeric substance manufacturing firm and mixed with polymers, and this product dissolves the back at the scene directly to be used.
When making liquid Tiorco 677 linking agent product, at first in reactor, add deionized water and citric acid and be mixed with 50% aqueous citric acid solution, the aluminum chloride (anhydrous or crystallization) that adds metering then, because Aluminum chloride anhydrous is hydrolyzed and replacement(metathesis)reaction than being easier in aqueous citric acid solution, emit hydrogenchloride, the preferential Aluminum chloride anhydrous that uses of suggestion.Be warming up to 95～105 ℃ of reactions more than two hours, the hydrogenchloride that displaces is water and aqueous sodium hydroxide solution absorption respectively.
Keeping under the good stirring state, 50% of the adding metering sodium aluminate solution is controlled total aluminum ion: citric acid=1.5: 1～2.2: 1 in above-mentioned reaction solution., stop heating and be cooled to 65～75 ℃ more than four hours 105～110 ℃ of reactions then; Add high alkali liquid and regulate above pH value of reactants between 5.5～8.5, be preferably in 6.5～7.0.High alkali liquid preferably uses 25～28% ammoniacal liquor.Remove by filter insolubles then and obtain aluminium composition 3.5～5.5% liquid Tiorco 677 linking agent products.
Aluminum chloride can use Aluminum chloride anhydrous or crystal aluminum chloride, and tendency adopts Aluminum chloride anhydrous.No matter adopt which kind of aluminum chloride, wherein iron ion content should be low as far as possible, and when using Aluminum chloride anhydrous, iron is (with FeCl
3Meter)≤0.05%; When using crystal aluminum chloride, iron (Fe)≤0.035%.Sodium aluminate uses Na
2O/Al
2O
3=1.2～1.5, content 36%～40%, iron (Fe
2O
3The sodium aluminate product of)≤0.008% is mixed with 50% aqueous solution and uses.The mol ratio of aluminum chloride and sodium aluminate can change between 3: 1～1: 1, and it is proper between 2: 1～1: 1, and is best at 1.5: 1 o'clock.
Embodiment
By following laboratory, industrial production example the present invention is demonstrated, illustrate that how making aluminium ion concentration is 3.5～5.5% (wt), pH value 6.5～7.5, aluminum ion: citric acid=1.9～2.0: 1 liquid cross-linker product and warp further drying make aluminium ion concentration 〉=10%, aluminum ion: citric acid=1.9～2.0: 1 solid linking agent product.
Embodiment 1:
Mechanical stirring is housed, reflux exchanger, the 1000mL four-hole boiling flask of thermometer places the temperature adjustment electrically heated of 1000mL to put, the stirring of adding 200g deionized water and 200g citric acid-water (0.927mol) is made into 50% the aqueous solution in flask, then 308g crystal aluminum chloride (1.237mol) is added in the four-hole boiling flask, be warming up to 95～105 ℃ of reactions more than two hours, the hydrogenchloride that displaces is water and aqueous sodium hydroxide solution absorption respectively.Keep the reactant boiling, progressively add 146.6g50% sodium aluminate (0.618mol) aqueous solution for preparing in advance in the four-hole boiling flask, adding along with sodium aluminate solution, reactant changes white soup compound into by clear solution gradually in the flask,, stop heating and be cooled to 65～75 ℃ more than four hours 105～110 ℃ of back flow reaction then.Keep under the good stirring state, the ammoniacal liquor of adding 25～28% is regulated above pH value of reactants 6.5～7.0.Remove by filter insolubles and obtain 1100g liquid Tiorco 677 linking agent product, aluminium composition 4.55%.
Embodiment 2:
Adopt as reaction unit among the embodiment 1 and technology, the add-on of crystal aluminum chloride and 50% sodium aluminate solution changes 292g (1.18mol) and 160g (0.674mol) respectively into, can get 1075g liquid Tiorco 677 linking agent product, aluminium composition 4.66%.
Embodiment 3:
Adopt as reaction unit among the embodiment 1 and technology, the add-on of crystal aluminum chloride and 50% sodium aluminate solution changes 230.7g (0.927mol) and 220g (0.927mol) respectively into, can get 1075g liquid Tiorco 677 linking agent product, aluminium composition 4.46%.
Embodiment 4:
Mechanical stirring is being housed, feeder for solid materials, reflux exchanger, adding 300kg deionized water and 425kg citric acid-water (2.004 kilomol) stir and are made into the aqueous solution in the 2000L electrically heated enamel reaction still of thermometer, then 615kg crystal aluminum chloride (2.420kmol) is added in the reactor, be warming up to 95～105 ℃ of reactions more than two hours, the hydrogenchloride that displaces is water and aqueous sodium hydroxide solution absorption respectively.Keep the reactant boiling, progressively add 450kg 50% sodium aluminate (1.588kmol) aqueous solution for preparing in advance in the reactor, adding along with sodium aluminate solution, the reaction kettle for reaction thing changes white soup compound into by clear solution gradually,, stop heating and be cooled to 65～75 ℃ more than four hours 105～110 ℃ of back flow reaction then.Keep under the good stirring state, the ammoniacal liquor of adding 25～28% is regulated above pH value of reactants 6.5～7.0.Remove by filter insolubles and obtain 2250kg liquid Tiorco 677 linking agent product, aluminium composition 4.80%.
Embodiment 5:
Mechanical stirring is being housed, feeder for solid materials, reflux exchanger, adding 500kg deionized water and 500kg citric acid-water (2.36kmol) stir and are made into the aqueous solution in the 2000L electrically heated enamel reaction still of thermometer, then 384kg Aluminum chloride anhydrous (2.832kmol) is added in the reactor, be warming up to 95～105 ℃ of reactions more than two hours, the hydrogenchloride that displaces is water and aqueous sodium hydroxide solution absorption respectively.Keep the reactant boiling, progressively add 530kg 50% sodium aluminate (1.871kmol) aqueous solution for preparing in advance in the reactor, adding along with sodium aluminate solution, the reaction kettle for reaction thing changes white soup compound into by clear solution gradually,, stop heating and be cooled to 65～75 ℃ more than four hours 105～110 ℃ of back flow reaction then.Keep under the good stirring state, the ammoniacal liquor of adding 25～28% is regulated above pH value of reactants 6.5～7.0.Remove by filter insolubles and obtain 2450kg liquid Tiorco 677 linking agent product, aluminium composition 5.18%.
Embodiment 6:
Liquid Tiorco 677 linking agent product by embodiment 4 gained 100g aluminium composition 4.80% obtains 45.5g white solid product, aluminium composition 10.55% through drying down at 80 ℃.The liquid Tiorco 677 linking agent product of the 100g aluminium composition 5.18% that embodiment 5 obtains obtains 42.5g white solid product, aluminium composition 12.19% through drying down at 80 ℃.The liquid Tiorco 677 linking agent product that this shows embodiment 1～5 gained adopts suitable technology to carry out drying, can obtain aluminium composition greater than 10.0% solid citric acid aluminium product.
Embodiment 7:
The liquid or solid Tiorco 677 linking agent preparation cross-linking polymer system of the present invention's preparation is adopted in the present embodiment explanation.Polymkeric substance adopts the partially hydrolyzed polyacrylamide that the grand celebration chemical general factory is produced, viscosity-average molecular weight 1,500 ten thousand, degree of hydrolysis 25～28% in the experiment.Adopt the 0.5%NaCl deionized water solution in the experiment, the cross-linking polymer system of the different poly-aluminum ratios of prepared polymer concentration 600mg/L by measuring the transistion pressure of difference cross-linking polymer system storage period, is estimated the sealing characteristics of cross-linking polymer system.Transistion pressure is U.S. Tiorco, Inc. can the shutoff porous medium in order to characterize formed gel,. employing interlaces with interlayer, and miter angle is placed, five layer of 100 order stainless steel mesh simulation porous medium of compacting, measures formed gel by the required minimal pressure that adds of simulation porous medium.The transistion pressure value is bigger, shows that the intensity of formed gel is bigger, and system is stronger to the shut-off capacity of porous medium.
Following data provide the data of the cross-linked polymer solution transistion pressure of the difference composition that uses the preparation of different aluminum content Tiorco 677 linking agent in different storage periods.
The transistion pressure (MPa) of the poly-aluminum ratio cross-linked polymer solution of linking agent
(Al
3+Content) 1 day 5 days 15 days 30 days
4.35％ 0.043 0.123 0.086 0.049
4.58％ 0.046 0.048 0.064 0.047
40∶1
5.33％ 0.044 0.164 0.083 0.045
10.55％ 0.010 0.118 0.073 0.044
The transistion pressure of linking agent cross-linked polymer solution (MPa)
Poly-aluminum ratio
(Al
3+Content) 1 day 3 days 7 days 20 days
20∶1 0.046 0.061 0.074 0.065
40∶1 0 0.053 0.076 0.070
4.80
60∶1 0 0.061 0.037 0.075
80∶1 0 0.058 0.065 0.072
Above data declaration is in the 600mg/L partially hydrolyzed polyacrylamide aqueous solution in concentration, add the Tiorco 677 linking agent that an amount of this patent is made, under the poly-aluminum ratio condition of broad (20: 1～80: 1), all form cross-linked polymer solution well with certain intensity.
Claims (4)
1. the preparation method of high-Al aluminium citrate cross-linking agent, aluminum ion is provided by anhydrous or crystalline aluminum chloride and sodium aluminate respectively, and its preparation process is as follows:
1.. citric acid and deionized water compound concentration are 50% aqueous citric acid solution;
2.. under agitation slowly add aluminum chloride, 95～105 ℃ of reactions 2 hours that heat up then, the hydrogenchloride that displaces is water and sodium hydroxide solution absorption respectively;
3.. under agitation add 50% sodium aluminate solution, control total aluminum ion,, stop heating, be cooled to 65～75 ℃ 105～110 ℃ of reactions 4 hours down than citric acid=1.5: 1～2.2: 1;
4.. under agitation, add high alkali liquid, make PH=5.5～8.5;
5.. remove by filter insolubles, obtain aluminium composition and be 3.5～5.5% liquid Tiorco 677 linking agent product;
6.. through super-dry, crystallization, obtain aluminium composition greater than 10% solid citric acid aluminum crosslinker product.
2. the preparation method of high-Al aluminium citrate cross-linking agent according to claim 1, it is characterized in that: the mol ratio that aluminum ions aluminum chloride and sodium aluminate are provided is 3: 1～1: 1.
3. the preparation method of high-Al aluminium citrate cross-linking agent according to claim 1 is characterized in that: the ammoniacal liquor of the high alkali liquid employing 25～28% that is added.
4. according to the preparation method of claim 1 and 3 described high-Al aluminium citrate cross-linking agents, it is characterized in that: add high alkali liquid ammoniacal liquor, the amount of its ammoniacal liquor reaches PH=6.5～7.0 that make reaction system.
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| CN 00135877 CN1117803C (en) | 2000-12-22 | 2000-12-22 | Process for preparing high-Al aluminium citrate cross-linking agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00135877 CN1117803C (en) | 2000-12-22 | 2000-12-22 | Process for preparing high-Al aluminium citrate cross-linking agent |
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| CN1117803C true CN1117803C (en) | 2003-08-13 |
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| CN102898299A (en) * | 2011-07-29 | 2013-01-30 | 中国石油天然气股份有限公司 | Method for synthesizing aluminum citrate cross-linking agent in low carbon solvent |
| CN104449614A (en) * | 2014-11-14 | 2015-03-25 | 天津大港油田滨港集团博弘石油化工有限公司 | Aluminum citrate water-plugging cross-linking agent for oil extraction |
| CN107722248A (en) * | 2017-10-17 | 2018-02-23 | 陈合华 | A kind of preparation method of fire resistant resin Anchor Agent |
| CN109364418A (en) * | 2018-11-26 | 2019-02-22 | 山东科技大学 | A kind of plastigel material for preventing and treating spontaneous combustionof coal |
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