CN113800653A - Geothermal fluid scale inhibitor and preparation method and application thereof - Google Patents
Geothermal fluid scale inhibitor and preparation method and application thereof Download PDFInfo
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- CN113800653A CN113800653A CN202010550478.7A CN202010550478A CN113800653A CN 113800653 A CN113800653 A CN 113800653A CN 202010550478 A CN202010550478 A CN 202010550478A CN 113800653 A CN113800653 A CN 113800653A
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- scale inhibitor
- geothermal fluid
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
Abstract
The invention discloses a geothermal fluid scale inhibitor and a preparation method and application thereof, and the geothermal fluid scale inhibitor comprises the following components in percentage by total weight: 10-12 wt% of organic phosphonic acid, 4-6 wt% of polymer salt, 2-6 wt% of polymer dispersant and the balance of water. The geothermal fluid scale inhibitor provided by the invention realizes the purpose of inhibiting calcium carbonate scaling and precipitation in a high-temperature flowing geothermal fluid state, and has an excellent scale inhibition effect.
Description
Technical Field
The invention belongs to the technical field of scale inhibitors, and particularly relates to a geothermal fluid scale inhibitor and a preparation method and application thereof.
Background
Terrestrial heat is clean energy which can be comprehensively utilized in a diversified way, and China has a mature technology in the aspect of terrestrial heat development and utilization. The geothermal energy can be used as a hot water source, a heat source and mineral resources, such as heating, power generation, showering, seed culture and the like, has low cost and high benefit in the utilization process, and has important significance for developing economy and preventing pollution.
However, geothermal fluids generally have a relatively high salt content. High salinity geothermal fluid is because pressure and temperature variation in exploitation and transportation process, takes place scale deposit and jam easily, causes the pressure grow of geothermal well and even causes well head fracture, equipment damage, heat exchange efficiency to descend, filtration system jam, a series of problems such as recharge effect descend, has restricted high-efficient utilization of geothermal resources and geothermal system's steady operation. The scaling problem of geothermal fluid has great influence on the normal operation of a geothermal utilization system, and becomes one of the most important problems in the process of restricting the development and utilization of geothermal resources.
The common type of geothermal fluid fouling is CaCO3The addition of scale inhibitors is one of the important and feasible ways to prevent scaling. The scale inhibitor is an effective means for preventing system scaling and ensuring long-term operation of equipment, and is widely used in water treatment. However, in the field of geothermal heat, a method of a scale inhibitor aiming at the characteristics of geothermal fluid has not been widely researched, and the conventional scale inhibitor in other industries has no applicability because the difference between the water quality and the working parameter range of fluid and the geothermal fluid is obvious. All in oneIn the process of mining and transporting geothermal water, the geothermal water is usually in a high-temperature state, and some scale inhibitors may lose effectiveness due to overhigh temperature in the high-temperature state, so that the effect of stabilizing scale inhibition cannot be achieved. Therefore, it is necessary to develop a scale inhibitor and a preparation method thereof aiming at the characteristics of geothermal fluid to make up the blank of the field and meet the scale inhibition requirement.
Disclosure of Invention
The invention aims to overcome the defects that a scale inhibitor suitable for characteristics of geothermal fluid is lack and the conventional scale inhibitor fails at high temperature, and provides a geothermal fluid scale inhibitor which can play a role in a geothermal fluid system, inhibit and disperse calcium carbonate precipitation, solve the problem of scaling and blocking of pipelines, equipment and a recharge well in a geothermal system, ensure stable operation of geothermal clean energy utilization projects, improve the utilization quality of geothermal energy and ensure the recharge effect.
In order to achieve the above object, a first aspect of the present invention provides a geothermal fluid scale inhibitor comprising, based on the total weight of the geothermal fluid scale inhibitor: 10-12 wt% of organic phosphonic acid, 4-6 wt% of polymer salt, 2-6 wt% of polymer dispersant and the balance of water.
The second aspect of the present invention provides a method for preparing the above-mentioned geothermal fluid scale inhibitor, comprising: and uniformly mixing the organic phosphonic acid, the polymer salt, the polymer dispersant and water to obtain the geothermal fluid scale inhibitor.
A third aspect of the invention provides the use of the above-described geothermal fluid scale inhibitor in a geothermal system.
The technical scheme of the invention has the following beneficial effects:
(1) the geothermal fluid scale inhibitor provided by the invention realizes the purpose of inhibiting calcium carbonate scaling and precipitation in a high-temperature flowing geothermal fluid state, and has an excellent scale inhibition effect.
(2) The geothermal fluid scale inhibitor has good high temperature resistance, and has good scale inhibition performance under the condition of maintaining at 90 ℃ for 10 hours. When the injection amount of the geothermal fluid scale inhibitor is 100mg/L, the scale inhibition rate of inhibiting calcium carbonate precipitation reaches over 90 percent. The compound scale inhibitor can still exert excellent scale inhibition performance after heat treatment, and is suitable for geothermal systems with local high-temperature areas.
(3) The geothermal fluid scale inhibitor has important significance for solving the problem of blockage caused by scaling of the wellhead, the pipeline, the heat exchanger and other parts of a geothermal system and ensuring long-period operation of the system.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
The first aspect of the present invention provides a geothermal fluid scale inhibitor comprising, based on the total weight of the geothermal fluid scale inhibitor: 10-12 wt% of organic phosphonic acid, 4-6 wt% of polymer salt, 2-6 wt% of polymer dispersant and the balance of water.
In the present invention, the water is preferably deionized water.
Preferably, the geothermal fluid scale inhibitor comprises, based on the total weight of the geothermal fluid scale inhibitor: 10 wt% of organic phosphonic acid, 5 wt% of polymer salt, 5 wt% of polymer dispersant and the balance of water.
The geothermal fluid scale inhibitor is mainly compounded by organic phosphonic acid, polymer salt and polymer dispersant. In the development process of geothermal water, carbon dioxide is separated out due to pressure change, calcium ions and calcium carbonate exceed the solubility product, and calcium carbonate precipitation is generated. The scale inhibitor can form a stable soluble chelate with calcium ions, reduce the collision and combination frequency of the calcium ions and carbonate ions, and improve the allowable concentration of the calcium ions; adsorbed and doped in lattice or on crystal interface to inhibit the growth of crystal seed or make the crystal seed not grow normally and crack; the chain structure of the scale inhibitor adsorbs a plurality of calcium carbonate crystal seeds with the same charge, and the electrostatic repulsion can prevent the calcium carbonate crystal seeds from further colliding with each other to form crystals with larger size. The organic phosphonic acid and the polymer salt scale inhibitor achieve the purpose of inhibiting the generation of calcium carbonate scale through the three scale inhibition mechanisms. The polymer dispersant is weakly adsorbed on the surface of a calcium carbonate crystal nucleus to form a surface negative electron layer, so that the van der Waals attraction force among the crystal nuclei is reduced, and the crystal nuclei are stably dispersed in a solution and are not easy to form crystals with larger sizes. The organic phosphonic acid, the polymer salt scale inhibitor and the polymer dispersant are compounded, and the effect of further enhancing the scale inhibition effect is realized through the coordination of the different mechanisms.
According to the invention, the organic phosphonic acid is preferably 2-phosphonobutane-1, 2, 4-tricarboxylic acid.
In the invention, 2-phosphonic butane-1, 2, 4-tricarboxylic acid (PBTCA) is one of organic phosphonic acid scale inhibitors with the lowest phosphorus content (containing 11.48 percent of phosphorus), has the characteristics of both phosphonic acid and carboxylic acid groups, and has obviously higher scale inhibition performance under high temperature conditions than other organic phosphonic acids.
According to the invention, preferably, the polymer salt is sodium polyaspartate.
According to the present invention, it is preferred that the weight average molecular weight of the polymer salt is 1000-4000.
In the invention, the sodium polyaspartate is a green polymer salt, has good scale inhibition effect and is easy to degrade by the environment.
According to the present invention, preferably, the polymeric dispersant is polyvinyl alcohol.
According to the invention, the degree of alcoholysis of the polymeric dispersant is preferably 88% or 99%.
In the present invention, the average polymerization degree of the polymer dispersant is 1700.
In the present invention, polyvinyl alcohol (PVA) can effectively disperse calcium carbonate grains.
The second aspect of the present invention provides a method for preparing the above-mentioned geothermal fluid scale inhibitor, comprising: and uniformly mixing the organic phosphonic acid, the polymer salt, the polymer dispersant and water to obtain the geothermal fluid scale inhibitor.
A third aspect of the invention provides the use of the above-described geothermal fluid scale inhibitor in a geothermal system.
According to the present invention, it is preferable that the above-mentioned geothermal fluid scale inhibitor is charged in an amount of 60 to 100mg with respect to 1L of geothermal water.
In the invention, when in use, the scale inhibitor is added in an amount of 60mg-100mg/L, and a person skilled in the art can automatically adjust the adding amount according to the concentration of calcium ions in actual geothermal water.
Preferably, the geothermal fluid scale inhibitor provided by the invention is suitable for geothermal water quality conditions as follows: the salinity of geothermal water is 6000-8000mg/L, wherein the concentration of calcium ions is 100-300mg/L, the concentration of bicarbonate ions is 100-400mg/L, and the other anions and cations are chloride ions, carbonate ions, nitrate ions, sulfate ions, sodium ions, magnesium ions, potassium ions and the like respectively; the pH of the geothermal water is 7.5-9.0.
The invention is further illustrated by the following examples:
the sodium polyaspartate used in the following examples and comparative examples had a weight average molecular weight of 1000, available from Shanghai-derived leaf Biotech, Inc. under the designation S25535; the polyvinyl alcohol has the average polymerization degree of 1700 and the alcoholysis degree of 99 percent, and is purchased from Shanghai Aladdin Biotechnology Co., Ltd under the brand number of P105126; the 2-phosphonobutane-1, 2, 4-tricarboxylic acid was obtained from Shanghai Allantin Biotechnology Ltd under the product designation P136293.
Example 1
The embodiment provides a scale inhibitor for geothermal fluid, which comprises the following specific preparation methods: adding 2g of butane phosphonate-1, 2, 4-tricarboxylic acid (PBTCA) and 4g of sodium polyaspartate (PASP) into a container with a certain volume, adding 80g of deionized water, heating to 50 ℃, and uniformly stirring; and then heating to 95 ℃ for maintenance, adding 6g of polyvinyl alcohol (PVA) solid powder, stirring for 4h, and obtaining the geothermal fluid scale inhibitor after the PVA is completely dissolved.
Example 2
The embodiment provides a scale inhibitor for geothermal fluid, which comprises the following specific preparation methods: adding 2g of butane-1, 2, 4-tricarboxylic acid (PBTCA) phosphonate and 5g of sodium polyaspartate (PASP) into a container with a certain volume, adding 80g of deionized water, heating to 50 ℃, and uniformly stirring. And then heating to 95 ℃ for maintenance, adding 5g of polyvinyl alcohol (PVA) solid powder, stirring for 4h, and obtaining the geothermal fluid scale inhibitor after the PVA is completely dissolved.
Example 3
The embodiment provides a scale inhibitor for geothermal fluid, which comprises the following specific preparation methods: adding 2g of butane-1, 2, 4-tricarboxylic acid (PBTCA) phosphonate and 5g of sodium polyaspartate (PASP) into a container with a certain volume, adding 80g of deionized water, heating to 50 ℃, and uniformly stirring. And then heating to 95 ℃ for maintaining, adding 3g of polyvinyl alcohol (PVA) solid powder, stirring for 4h, and obtaining the geothermal fluid scale inhibitor after the PVA is completely dissolved.
Example 4
The embodiment provides a scale inhibitor for geothermal fluid, which comprises the following specific preparation methods: adding 2g of butane-1, 2, 4-tricarboxylic acid (PBTCA) phosphonate and 6g of sodium polyaspartate (PASP) into a container with a certain volume, adding 80g of deionized water, heating to 50 ℃, and uniformly stirring. And then heating to 95 ℃ for maintenance, adding 2g of polyvinyl alcohol (PVA) solid powder, stirring for 4h, and obtaining the geothermal fluid scale inhibitor after the PVA is completely dissolved.
Comparative example 1
The comparative example provides a geothermal fluid scale inhibitor, and the specific preparation method comprises the following steps: adding 2g of butane phosphonate-1, 2, 4-tricarboxylic acid (PBTCA) into a container with a certain volume, adding 80g of deionized water, heating to 50 ℃, and uniformly stirring to obtain the geothermal fluid scale inhibitor.
Comparative example 2
The comparative example provides a geothermal fluid scale inhibitor, and the specific preparation method comprises the following steps: and (3) adding 20g of Polyaspartic Acid Sodium (PASP) into a container with a certain volume, adding 80g of deionized water, heating to 50 ℃, and uniformly stirring to obtain the geothermal fluid scale inhibitor.
Comparative example 3
The comparative example provides a geothermal fluid scale inhibitor, and the specific preparation method comprises the following steps: adding 80g of deionized water into a container with a certain volume, heating to 95 ℃ for maintaining, adding 20g of polyvinyl alcohol (PVA), stirring for 4 hours, and obtaining the geothermal fluid scale inhibitor after the PVA is completely dissolved.
Test example
Carrying out scale inhibition effect evaluation on the scale inhibitors prepared in the examples and the comparative examples, wherein the dynamic scale inhibition performance of calcium carbonate refers to GB/T16632-2008, sampling to obtain geothermal water before heating, adding the scale inhibitor to heat the geothermal water for 10 hours, and not adding the scale inhibitor to heat the geothermal water for 10 hours; respectively testing the calcium ion concentration by using an ion chromatograph, and calculating the scale inhibition rate eta, eta ═ C2-C3)/(C1-C3) X 100%, wherein the parameters are the original calcium ion concentration C before the experiment of the geothermal water sample (i.e. geothermal water before heating)1After the scale inhibitor is added, the calcium ion concentration C is measured (namely the geothermal water after the scale inhibitor is added and heated for 10 hours)2After the experiment without adding the scale inhibitor (i.e. the geothermal water after heating for 10h without adding the scale inhibitor), the calcium ion concentration C3。
The salinity of the geothermal water used in the test is 6000mg/L, wherein the concentration of calcium ions is 175mg/L, the concentration of bicarbonate ions is 289mg/L, and the rest anions and cations are chloride ions, carbonate ions, nitrate ions, sulfate ions, sodium ions, magnesium ions, potassium ions and the like respectively; the pH value of the geothermal water is 8.6, and the addition amount of the scale inhibitor is 60-100mg/L (see table 1 specifically). In the specific implementation process, the geothermal water sample circularly flows in the pipeline under the driving of the peristaltic pump, and the flowing speed is 0.48 m/s. The water bath heating was maintained at 90 ℃ for 10 h. Adopt the silica gel hose as geothermal water flow pipe, use the water bath to heat the pipeline during the experiment, geothermal water flows through the hose and can be heated to 90 ℃. The heat treatment in Table 1 was carried out by heating the scale inhibitor at 120 ℃ for 3 hours in a hydrothermal kettle before use. After the experiment is finished, the scale inhibition performance is evaluated by measuring the concentration of calcium ions in the geothermal water and calculating the scale inhibition rate eta. The results of the experiment are shown in table 1.
Table 1 scale inhibition performance test results
| Serial number | Addition amount of scale inhibitor (mg/L) | Whether or not to heat-treat | Calcium carbonate Scale inhibition rate eta (%) |
| Example 1 | 60 | Whether or not | 81.1 |
| Example 1 | 100 | Whether or not | 91.6 |
| Example 2 | 100 | Whether or not | 94.1 |
| Example 2 | 100 | Is that | 85.3 |
| Example 3 | 100 | Whether or not | 92.2 |
| Example 4 | 100 | Whether or not | 91.5 |
| Comparative example 1 | 60 | Whether or not | 71.9 |
| Comparative example 1 | 100 | Whether or not | 75.3 |
| Comparative example 2 | 100 | Whether or not | 62.4 |
| Comparative example 3 | 100 | Whether or not | 46.7 |
As can be seen from the results in the table, when the adding amount of the geothermal fluid scale inhibitor used in the invention is 100mg/L, the scale inhibition rate on calcium carbonate reaches over 90 percent, and after high-temperature heat treatment, the scale formation of the geothermal water calcium carbonate can be effectively prevented. From a comparison of the examples and comparative examples, it can be seen that: under the same concentration, the effect of the compound scale inhibitor is obviously better than that of any one single-component scale inhibitor, and the synergistic effect of different functional group scale inhibitors is reflected.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (9)
1. A geothermal fluid scale inhibitor, which is characterized by comprising the following components in percentage by weight based on the total weight of the geothermal fluid scale inhibitor: 10-12 wt% of organic phosphonic acid, 4-6 wt% of polymer salt, 2-6 wt% of polymer dispersant and the balance of water.
2. The geothermal fluid scale inhibitor according to claim 1, wherein the organophosphonic acid is 2-phosphonobutane-1, 2, 4-tricarboxylic acid.
3. The geothermal fluid scale inhibitor according to claim 1, wherein the polymer salt is sodium polyaspartate.
4. The geothermal fluid scale inhibitor according to claim 1, wherein the polymer salt has a weight average molecular weight of 1000-4000.
5. The geothermal fluid scale inhibitor according to claim 1, wherein the polymeric dispersant is polyvinyl alcohol.
6. The geothermal fluid scale inhibitor according to claim 1, wherein the polymer dispersant has an alcoholysis degree of 88% or 99%.
7. The method for preparing a scale inhibitor for geothermal fluid according to any one of claims 1 to 6, comprising: and uniformly mixing the organic phosphonic acid, the polymer salt, the polymer dispersant and water to obtain the geothermal fluid scale inhibitor.
8. Use of a geothermal fluid scale inhibitor according to any one of claims 1 to 6 in a geothermal system.
9. The use according to claim 8, wherein the geothermal fluid scale inhibitor is dosed in an amount of 60-100mg per 1L of geothermal water.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115011314A (en) * | 2022-07-22 | 2022-09-06 | 山东省地质矿产勘查开发局第二水文地质工程地质大队(山东省鲁北地质工程勘察院) | Preparation and application of fluorescent carbon quantum dots for scale inhibition of geothermal fluid |
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