CN111154469A - Synthetic method of organic chromium composite salt for complexing and crosslinking - Google Patents
Synthetic method of organic chromium composite salt for complexing and crosslinking Download PDFInfo
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- CN111154469A CN111154469A CN201911415395.0A CN201911415395A CN111154469A CN 111154469 A CN111154469 A CN 111154469A CN 201911415395 A CN201911415395 A CN 201911415395A CN 111154469 A CN111154469 A CN 111154469A
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- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/512—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
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- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
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- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
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- C09K8/685—Compositions based on water or polar solvents containing organic compounds containing cross-linking agents
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Abstract
The invention relates to a synthetic method of organic chromium composite salt for complexing and crosslinking, which mainly comprises the following steps: 1) sequentially adding water, chromic anhydride, propionic acid and masking agent into a reactor with condensing reflux, stirring at 40-60 ℃, and preheating; 2) mixing water, a reducing agent, a masking agent and a certain amount of propionic acid; 3) adding the mixed solution prepared in the step 2) into the solution prepared in the step 1), continuously stirring, controlling the reaction temperature to be 60-90 ℃, condensing, refluxing and recycling at 50-60 ℃, continuously reacting, and after the solution prepared in the step 2) is reacted and added, continuously keeping stirring, heat preservation and refluxing for a curing reaction for 0.5-1h, and naturally cooling for 1-2 h; 5) adding stress resistance agent into the finished product of the step 4), and stirring for 5-10min to obtain the product. The synthetic method of the invention adopts general raw materials, popular process, reasonable dispersion reaction process, perfection of key factors influencing quality and efficiency, improvement of stability, simple operation and wide product application range.
Description
Technical Field
The invention relates to the field of oil exploitation, in particular to a synthesis method of an organic chromium crosslinking agent for profile control, fracturing and oil displacement.
Background
Sodium dichromate, sodium chromate and other hexavalent chromium are used in the field of cross-linking agents for oil extraction, water injection and profile control, and the effect is excellent, but the strong oxidizing property and the high toxicity of the hexavalent chromium limit the use of the hexavalent chromium, particularly the hexavalent chromium belongs to one of internationally recognized carcinogens, and the fear of using the hexavalent chromium is increased. The use of hexavalent chromium based cross-linking agents has been banned.
When the trivalent chromium is used for oil extraction profile control crosslinking, the influence of the valence state of the chromium salt and the composition of a compound is large, wherein the reaction speed of inorganic chromium salts with the trivalent state, such as chromium chloride, chromium sulfate, chromium nitrate and the like, is too high no matter the inorganic chromium salts are used independently or used in a mixed way, and the effects of delaying crosslinking and uniformly crosslinking are not good; the organic chromium acid is also greatly influenced by ionization decomposition of the complex and complex acid radicals, and compared with a common chromium acetate product, the universality of the organic chromium stable solution is more time-consuming and deeply profile-controlling, and meanwhile, the environmental temperature, mineralization influence and hybridization stability are improved, so that the organic chromium acid is one of green schemes worthy of popularization in the future.
Meanwhile, chromium is also considered to be one of trace elements necessary for human and animals, and trivalent chromium salt, particularly complex chromium separated from organic acid salt is an element necessary for insulin to play a role in the glucose metabolism process, and is widely applied to the aspects of controlling human type II diabetes mellitus and animal feed additives by therapy, particularly replacing and breeding clenbuterol. Therefore, stable trivalent chromium salts, especially organic acid chromium salts, are beneficial to human beings within a reasonable metering and control range.
At present, the research aiming at organic chromium is few in the field of oil extraction, the society mainly focuses on the use and tracking effects of human health care products and livestock and poultry additives, and the synthetic research bulletins related to high-quality products are few, and the following four types are mainly included: firstly, according to the traditional method, high-valence chromium compounds such as dichromate, chromate, chromic anhydride and the like are reduced and then complexed with organic acid such as propionic acid and the like, and the solution is separated, concentrated and crystallized or is directly used. The other is formed by directly reacting and complexing inorganic salt of trivalent chromium such as chromium sulfate, chromium chloride, chromium nitrate and the like with propionic acid. And thirdly, chromium-containing waste residues, waste mud and the like are crushed or dispersed, and chromium is enriched by adopting methods of water dissolving, acid leaching, reduction, separation and the like and then is complexed with propionic acid and the like to obtain the chromium-enriched chromium-. Fourthly, the rough ferrochrome or the metal chromic acid is dissolved and homogenized and then reacts with propionic acid to prepare the chromium-containing iron. The examination of domestic patents needs to gradually schedule the indexes of environmental protection, health and comprehensive sustainable resource utilization on the basis of improving the formula and stabilizing the process.
Disclosure of Invention
The invention aims to innovate the product synthesis technology and the application field, and provides a synthesis method of main salt organic chromium for oil extraction profile control crosslinking.
A synthetic method of organic chromium composite salt for crosslinking at least comprises the following steps:
1) sequentially adding water, chromic anhydride, propionic acid and masking agent into a reactor with condensation reflux according to a certain proportion, stirring, preheating and controlling the temperature to be 40-60 ℃; wherein the molar ratio of water, chromic anhydride and propionic acid is 40-80: 1-2: 1 to 6;
2) mixing water, a reducing agent, a masking agent and a certain amount of propionic acid, and transferring the mixture into a container according to the whole reaction proportion; wherein the molar part ratio of the water to the reducing agent to the propionic acid mixed solution is 40-80: 1-5: 0 to 10; the container is a high-position tank, a horizontal tank or a low-position tank; the addition amount of the masking agent is 0-10% of the mixed solution;
3) stably adding the mixed solution prepared in the step 2) into the solution prepared in the step 1) according to the flow rate, continuously stirring, controlling the reaction temperature to be 60-90 ℃, simultaneously opening a condensation reflux device, carrying out reflux recovery at 50-60 ℃, and continuing to react;
4) after the solution in the step 2) is reacted and added, continuing to keep stirring, preserving heat and performing reflux curing reaction for 0.5-1h, and naturally cooling for 1-2 h;
5) adding stress resistance agent into the product obtained in the step 4), and stirring for 5-10min to obtain the stress resistance agent, wherein the addition amount of the stress resistance agent is 0-0.1 wt% of the product obtained in the step 4).
In the above technical solution, in the step 1, the mass concentration of chromic anhydride in the chromic anhydride mixed solution is preferably 10-20%.
The masking agent is preferably one or more of sulfuric acid, sulfurous acid, hydrochloric acid, nitric acid, nitrous acid, oxalic acid, citric acid, gluconic acid, formic acid, acetic acid, pyridine carboxylic acid, humic acid and organic acid salts thereof.
The stress resistance agent is one or more of copper sulfate, zinc sulfate, sodium nitrite, sodium humate, potassium humate, acrylic acid and derivatives thereof.
Compared with the traditional technology, the synthesis method of the organic chromium crosslinking agent provided by the invention is innovative as follows:
1. the synthesis method of the invention adopts chromic anhydride, reducing agent and propionic acid as main reactants, and no additional inorganic acid radical and metal cation are added, thus promoting the stability of salt resistance of the finished product by relative purification reaction and overcoming the defect that inorganic acid radical ions influence the over-speed of cross-linking in the later period.
2. The chromic anhydride premixed solution and the reducing agent base dispersion solution are respectively stored after being pre-treated in two steps, chromium-containing substances are prevented from being diffused, the chromic anhydride premixed solution and the reducing agent base dispersion solution are added in proportion for reaction, volatile substances are condensed and recycled, and comprehensive utilization of effective reactants is increased while over-speed reaction is avoided.
3. The synthesis method adopts masking agent to effectively disperse and moderate the complex reaction of propionate and trivalent ions of metal chromium, and optimizes the deep crosslinking or delayed crosslinking reaction of the product in later period in use.
4. The synthesis method of the invention adopts the stress inhibitor to effectively inhibit the reversion of hexavalent chromium and the stability of a single cross-linking agent, and realizes the stress resistance and stability brought by long-distance transportation, temperature change and long-term storage.
5. The synthetic method is lower than normal boiling point reaction, increases volatile recovery, does not generate waste water, waste gas and waste residue, does not have hexavalent chromium residue, is environment-friendly, and can realize comprehensive utilization.
Detailed Description
The technical scheme of the invention is further explained by the specific examples.
Example 1
Step 1: sequentially adding 150 g of water, 50 g of chromic anhydride and 111 g of propionic acid into a reactor with condensation reflux, stirring, preheating and controlling the temperature to be 60 ℃;
step 2: 245 g of water, 6 g of reducing agent methanol and 3 g of masking agent citric acid are mixed and transferred to a high-level container for later use;
and step 3: slowly dripping the mixed solution prepared in the step 2 into the solution prepared in the step 1, continuously stirring, controlling the reaction temperature to be 70 ℃, simultaneously opening a condensation reflux device, refluxing and recovering at 60 ℃, continuously reacting, and controlling the dripping time to be 1 hour;
and 4, step 4: after the solution in the step (2) is reacted and added, continuing to keep stirring, preserving heat and performing reflux curing reaction for 1h, and naturally cooling for 1 h;
and 5: and (4) adding 0.5 g of zinc sulfate serving as a stress resistance agent into the finished product obtained in the step (4), and stirring for 10min, thus finishing the process.
Example 2
A synthesis method of an organic chromium crosslinking agent at least comprises the following steps:
step 1: sequentially adding 200 g of water, 50 g of chromic anhydride and 50 g of propionic acid into a reactor with condensation reflux, stirring, preheating and controlling the temperature to be between 50 ℃;
step 2: 195 g of water, 6 g of reducing agent methanol, 4 g of masking agent hydrochloric acid and 61 g of propionic acid are mixed and transferred into a high-level container for later use;
and step 3: slowly dripping the mixed solution prepared in the step 2 into the solution prepared in the step 1, continuously stirring, controlling the reaction temperature to be 80 ℃, simultaneously opening a condensation reflux device, refluxing and recovering at 50 ℃, continuously reacting, and controlling the dripping time to be 1.5 hours;
and 4, step 4: after the solution in the step 2 is reacted and added, continuing to keep stirring, preserving heat and performing reflux curing reaction for 0.5h, and naturally cooling for 1.5 h;
and 5: and (4) adding 0.4 g of stress-resistant potassium humate into the finished product in the step (4) in proportion, and stirring for 10min to finish the process.
Example 3
A synthesis method of an organic chromium crosslinking agent at least comprises the following steps:
step 1: sequentially adding 250 g of water, 50 g of chromic anhydride and 30 g of propionic acid into a reactor with condensation reflux according to a ratio, stirring, preheating and controlling the temperature to be 50 ℃;
step 2: mixing 145 g of water, 6 g of reducing agent methanol, 3 g of masking agent oxalic acid and 81 g of propionic acid, and transferring the mixture into a high-level container for later use;
and step 3: slowly dripping the mixed solution prepared in the step 2 into the solution prepared in the step 1, continuously stirring, controlling the reaction temperature to be 90 ℃, simultaneously opening a condensation reflux device, refluxing and recovering at 50 ℃, continuously reacting, and controlling the dripping time to be 2 hours;
and 4, step 4: after the solution in the step (2) is reacted and added, continuing to keep stirring, preserving heat and performing reflux curing reaction for 0.5h, and naturally cooling for 1 h;
and 5: and (4) adding 0.3 g of stress-resistant agent sodium humate into the finished product in the step (4) in proportion, and stirring for 5min to finish the process.
It should be emphasized that the above-described examples, while indicating certain embodiments of the invention, are given by way of illustration and description of preferred embodiments of the invention, and that these examples are not intended to limit the invention to the particular embodiments described, but rather are to be construed in an illustrative and non-restrictive manner, and that many alternatives, modifications, and variations of the invention are possible without departing from the spirit and scope of the invention.
Claims (4)
1. A synthetic method of organic chromium composite salt for complexing and crosslinking is characterized by at least comprising the following steps:
1) sequentially adding water, chromic anhydride, propionic acid and masking agent into a reactor with condensation reflux according to a certain proportion, stirring, preheating and controlling the temperature to be between 40 and 60 ℃; wherein the molar ratio of water, chromic anhydride and propionic acid is 40-80: 1-2: 1 to 6;
2) mixing water, a reducing agent, a masking agent and a certain amount of propionic acid, and transferring the mixture into a container according to the whole reaction proportion; wherein the molar part ratio of the water to the reducing agent to the propionic acid mixed solution is 40-80: 1-5: 0 to 10; the container is a high-position tank, a horizontal tank or a low-position tank; the addition amount of the masking agent is 0-10% of the mixed solution;
3) stably adding the mixed solution prepared in the step 2) into the solution prepared in the step 1) according to the flow rate, continuously stirring, controlling the reaction temperature to be 60-90 ℃, simultaneously opening a condensation reflux device, carrying out reflux recovery at 50-60 ℃, and continuing to react;
4) after the solution in the step 2) is reacted and added, continuing to keep stirring, preserving heat and performing reflux curing reaction for 0.5-1h, and naturally cooling for 1-2 h;
5) adding stress resistance agent into the product obtained in the step 4), and stirring for 5-10min to obtain the stress resistance agent, wherein the addition amount of the stress resistance agent is 0-0.1 wt% of the product obtained in the step 4).
2. The method for synthesizing organic chromium complex salt for complex crosslinking according to claim 1, wherein in the step 1, the mass concentration of chromic anhydride in the chromic anhydride mixed solution is 10 to 20%.
3. The method for synthesizing organic chromium complex salt for complex crosslinking according to claim 1, wherein in the step 2, the masking agent is a mixture of one or more of sulfuric acid, sulfurous acid, hydrochloric acid, nitric acid, nitrous acid, oxalic acid, citric acid, gluconic acid, formic acid, acetic acid, pyridine carboxylic acid, humic acid, and organic acid salts thereof.
4. The method for synthesizing organic chromium complex salt for complexing and crosslinking as claimed in claim 1, wherein said stress-resistant agent is a mixture of one or more of copper sulfate, zinc sulfate, sodium nitrite, sodium humate, potassium humate, acrylic acid and its derivatives.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86100473A (en) * | 1985-03-11 | 1986-10-01 | 菲利普石油公司 | The propionate-sequestered chromium (III) that produces with nitrite-dichromate redox reaction improves the rate of permeation contrast |
| CN104449615A (en) * | 2014-11-21 | 2015-03-25 | 天津大港油田滨港集团博弘石油化工有限公司 | Organic acid chromium crosslinking agent for oil production and preparation method thereof |
| CN108147961A (en) * | 2018-01-16 | 2018-06-12 | 四川新美生物科技有限公司 | A kind of preparation method of chromium propionate |
| CN110156587A (en) * | 2019-04-15 | 2019-08-23 | 四川尚元惠生生物科技有限公司 | A kind of technique of chromic acid chromium synthesis chromic formate |
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- 2019-12-31 CN CN201911415395.0A patent/CN111154469A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86100473A (en) * | 1985-03-11 | 1986-10-01 | 菲利普石油公司 | The propionate-sequestered chromium (III) that produces with nitrite-dichromate redox reaction improves the rate of permeation contrast |
| CN104449615A (en) * | 2014-11-21 | 2015-03-25 | 天津大港油田滨港集团博弘石油化工有限公司 | Organic acid chromium crosslinking agent for oil production and preparation method thereof |
| CN108147961A (en) * | 2018-01-16 | 2018-06-12 | 四川新美生物科技有限公司 | A kind of preparation method of chromium propionate |
| CN110156587A (en) * | 2019-04-15 | 2019-08-23 | 四川尚元惠生生物科技有限公司 | A kind of technique of chromic acid chromium synthesis chromic formate |
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