Composite corrosion and scale inhibitor composition, composite corrosion and scale inhibitor and preparation method and application thereof, and method for inhibiting corrosion and scale of geothermal water

Abstract

The present application relates to the field of geothermal water corrosion and scale inhibition, and in particular to a composite corrosion and scale inhibitor composition, a composite corrosion and scale inhibitor, a preparation method and application thereof, and a geothermal water corrosion and scale inhibition method, wherein the composition contains the following components: a phenylethyl quaternary phosphonium salt, a polymer A, a gluconate, an organic phosphine compound, an inorganic base, a water-soluble inorganic zinc salt, and water. The composite corrosion and scale inhibitor provided by the present application has good corrosion and scale inhibition effect in a geothermal water system with medium and low temperature and an oxygen-containing environment.

Description

Technical Field

[0001] The present invention relates to the field of geothermal water corrosion and scale inhibition, and in particular to a composite corrosion and scale inhibitor composition, a composite corrosion and scale inhibitor, a preparation method and application thereof, and a geothermal water corrosion and scale inhibition method. Background Art

[0002] With the rapid consumption of non-renewable resources such as oil and natural gas, geothermal energy has attracted increasing attention as a new energy source with broad development prospects.

[0003] Geothermal energy is a source of energy that can be used for various industrial and agricultural applications, including heating, power generation, cooling, healthcare, bathing, and aquaculture. Geothermal fluids include geothermal water, a two-phase mixture of geothermal water and steam, and geothermal steam.

[0004] The chemical composition of geothermal fluids is highly complex, containing corrosive components such as dissolved oxygen and chloride ions, and scaling components such as calcium ions and silica. The resulting corrosion and scaling of geothermal equipment, pipelines, and fittings hinders the efficient and economical use of geothermal energy. In addition to the properties of the geothermal fluid, corrosion and scaling are also affected by operating conditions such as temperature and pressure, as well as the materials used in the equipment.

[0005] Medium- and low-temperature (30-140°C) geothermal water contains corrosive gases such as dissolved oxygen, carbon dioxide and hydrogen sulfide, corrosive ions such as chloride ions and sulfate ions, scaling ions such as calcium ions and magnesium ions, and anaerobic or aerobic microorganisms such as sulfate-reducing bacteria, making corrosion and scaling of the system more difficult to control.

[0006] At present, there are mainly the following methods to control corrosion in the process of geothermal water utilization:

[0007] (1) Select corrosion-resistant materials: In addition to non-metallic materials (such as PVC-U plastic pipes), high-alloy stainless steel, nickel-based alloys, titanium alloys, zirconium and other metal materials that are resistant to geothermal corrosion can also be selected to increase the reliability of the geothermal system;

[0008] (2) Modified coating on metal substrate: A corrosion-resistant coating is applied to the surface of cheap metal to increase the corrosion resistance of the metal. Currently, such coatings mainly include polyphenylene sulfide-based coatings, metal ceramic coatings, micro-nano SiO2 coatings, etc.

[0009] (3) Adding chemical corrosion inhibitors: According to the working conditions of geothermal water, the relevant anti-corrosion agents mainly include sodium tripolyphosphate and hydrolyzed polymaleic anhydride;

[0010] (4) Cathodic protection: Use sacrificial anode method to provide electrochemical corrosion protection for equipment;

[0011] (5) Pretreatment such as washing before geothermal utilization: Use pretreatment processes such as washing to remove corrosive gases and corrosive ions in geothermal fluids.

[0012] At present, there are mainly the following methods to achieve scale inhibition in the process of geothermal water utilization:

[0013] (1) Add chemical antiscalant;

[0014] (2) Pretreatment and descaling before geothermal utilization or reinjection;

[0015] (3) Applying physical field to remove scale;

[0016] (4) Use anti-scaling coating;

[0017] (5) Use system pressurization method to prevent scale.

[0018] Due to the high price of corrosion-resistant materials, the coating anti-corrosion has not yet solved the problem of weak bonding between the coating and the substrate due to the different yield stresses between metal substrates such as carbon steel and the coating (especially organic coating), the application of chemical agents should be restricted from the perspective of environmental protection, the selection of electrode materials and process operations, etc., the corrosion and scaling problem in the process of geothermal water utilization has not been well solved, making the corrosion and scaling problem of geothermal systems a bottleneck in the development and utilization of geothermal resources.

[0019] At present, in the field of geothermal water corrosion and scale inhibition, there are no environmentally friendly corrosion and scale inhibitors for medium and low temperature (30-140°C) and oxygen-containing environments.

[0020] The corrosion and scaling problems of geothermal water systems in medium and low temperature, oxygen-containing environments are mainly manifested in high mineralization, a certain mass concentration of dissolved oxygen and carbon dioxide, and microorganisms such as sulfate-reducing bacteria. They have strong corrosion and scaling properties and are more difficult to control.

[0021] Therefore, in order to solve the above-mentioned existing technical problems, it is necessary to develop environmentally friendly corrosion and scale inhibitors for geothermal water systems in medium and low temperature and oxygen-containing environments. Summary of the Invention

[0022] The purpose of the present invention is to overcome the defect that the existing geothermal water corrosion and scale inhibition technology is difficult to effectively inhibit corrosion and scale in medium and low temperature and oxygen-containing environments.

[0023] Currently, there are no known methods for using fungicides for corrosion and scale inhibition in geothermal water. Drawing on methods for treating oilfield produced water, the inventors of the present invention have added commonly used oxidizing fungicides, quaternary ammonium salt fungicides, and quaternary phosphonium salt fungicides to corrosion and scale inhibitors used in geothermal water systems operating in medium- to low-temperature, oxygen-containing environments. Their research revealed that the phenethyl quaternary phosphonium salt provided by the present invention exhibits the best corrosion inhibition effect. In light of this, the inventors have developed the present invention.

[0024] In order to achieve the above object, the first aspect of the present invention provides a composite corrosion and scale inhibitor composition, which contains the following components: phenethyl quaternary phosphonium salt, polymer A, gluconate, organic phosphine compound, inorganic base, water-soluble inorganic zinc salt and water;

[0025] Relative to 100 parts by weight of the composite corrosion inhibitor and scale inhibitor composition, the content of the phenethyl quaternary phosphonium salt is 10-30 parts by weight, the content of the polymer A is 2-15 parts by weight, the content of the gluconate is 2-12 parts by weight, the content of the organic phosphine compound is 2-8 parts by weight, the content of the inorganic base is 2-13 parts by weight, the content of the water-soluble inorganic zinc salt is 2-12 parts by weight, and the content of water is 10-80 parts by weight;

[0026] Wherein, the phenethyl quaternary phosphonium salt has a structure shown in formula (1),

[0027]

[0028] In formula (1), X is halogen, and n is 12, 13, 14, 15 or 16;

[0029] The polymer A is selected from at least one of polyaspartic acid, polyepoxysuccinic acid and hydrolyzed polymaleic anhydride;

[0030] The organic phosphine compound is 2-hydroxyphosphonoacetic acid and / or 2-phosphono-1,2,4-tricarboxylic acid butane.

[0031] The second aspect of the present invention provides a method for preparing a composite corrosion inhibitor and scale inhibitor, the method comprising: mixing the components of the composite corrosion inhibitor and scale inhibitor composition described in the first aspect;

[0032] Preferably, the mixing conditions at least meet the following requirements: temperature of 10-30° C., time of 0.5-1 h, and stirring speed of 60-90 rpm.

[0033] The third aspect of the present invention provides a composite corrosion inhibitor and scale inhibitor prepared by the method described in the second aspect.

[0034] The fourth aspect of the present invention provides the use of the composite corrosion inhibitor and scale inhibitor described in the third aspect in geothermal water corrosion inhibition and scale inhibition.

[0035] A fifth aspect of the present invention provides a method for geothermal water corrosion and scale inhibition, the method comprising: adding the composite corrosion and scale inhibitor described in the third aspect to the geothermal water before the geothermal water comes out of the well.

[0036] Compared with existing geothermal water corrosion and scale inhibition technologies, the composite corrosion and scale inhibitor provided by the present invention has at least the following advantages:

[0037] The composite corrosion and scale inhibitor provided by the present application has good corrosion and scale inhibition effect in geothermal water system in low and medium temperature and oxygen-containing environment.

[0038] Other features and advantages of the present application will be described in detail in the following specific embodiments. DETAILED DESCRIPTION

[0039] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The endpoints of the ranges and the values are approximate values and should be understood to include values approximately near these ranges and values within these ranges. For ranges with endpoints, the endpoints are included in the ranges. For ranges without endpoints, the range extends to include any value approximately near the recited range. For ranges with endpoints and separate points, the endpoints and separate points are included in the ranges.

[0040] It should be noted that in aspects of the present application, the present application is described only once in one aspect for the same component in aspects, and the skilled in the art should not understand it as a limitation of the present application.

[0041] As described above, the first aspect of the present application provides a composite corrosion and scale inhibitor composition, which contains the following components: a phenethyl quaternary phosphonium salt, a polymer A, a gluconate, an organic phosphine compound, an inorganic base, a water-soluble inorganic zinc salt and water;

[0042] The content of the phenethyl quaternary phosphonium salt is 10-30 parts by weight, the content of the polymer A is 2-15 parts by weight, the content of the gluconate is 2-12 parts by weight, the content of the organic phosphine compound is 2-8 parts by weight, the content of the inorganic base is 2-13 parts by weight, the content of the water-soluble inorganic zinc salt is 2-12 parts by weight, and the content of the water is 10-80 parts by weight, relative to 100 parts by weight of the composite corrosion and scale inhibitor composition;

[0043] The phenethyl quaternary phosphonium salt has a structure shown in formula (1),

[0044]

[0045] In formula (1), X is halogen, and n is 12, 13, 14, 15 or 16;

[0046] The polymer A is at least one selected from polyaspartic acid (PASP), polyepoxysuccinic acid (PESA) and hydrolyzed polymaleic anhydride (HPMA);

[0047] The organic phosphine compound is 2-hydroxyphosphonoacetic acid (HPAA) and / or 2-phosphono-1,2,4-tricarboxylic acid butane (PBTC).

[0048] Preferably, relative to 100 parts by weight of the composite corrosion inhibitor and scale inhibitor composition, the content of the phenethyl quaternary phosphonium salt is 12-25 parts by weight, the content of the polymer A is 5-10 parts by weight, the content of the gluconate is 5-10 parts by weight, the content of the organic phosphine compound is 4-6 parts by weight, the content of the inorganic base is 5-10 parts by weight, the content of the water-soluble inorganic zinc salt is 4-9 parts by weight, and the content of water is 30-65 parts by weight.

[0049] Preferably, in formula (1), X is a chlorine element or a bromine element.

[0050] More preferably, in formula (1), X is chlorine, and n is 12, 14 or 16. The inventors have found that the composite corrosion and scale inhibitor obtained by adopting the specific embodiment of this preferred embodiment can have better corrosion and scale inhibition effect.

[0051] Preferably, the gluconate is selected from at least one of sodium gluconate, potassium gluconate, sodium D-gluconate, potassium D-gluconate, zinc gluconate and manganese gluconate.

[0052] Preferably, the inorganic base is selected from at least one of sodium hydroxide and potassium hydroxide.

[0053] Preferably, the water-soluble inorganic zinc salt is selected from at least one of zinc chloride, zinc nitrate and zinc sulfate.

[0054] As mentioned above, the second aspect of the present invention provides a method for preparing a composite corrosion inhibitor and scale inhibitor, which comprises: mixing the components of the composite corrosion inhibitor and scale inhibitor composition described in the first aspect.

[0055] Preferably, the mixing conditions at least meet the following requirements: temperature of 10-30° C., time of 0.5-1 h, and stirring speed of 60-90 rpm.

[0056] Preferably, the amount of each component in the composite corrosion inhibitor and scale inhibitor composition is controlled so that the content of phosphate in the prepared composite corrosion inhibitor and scale inhibitor is less than 2% by weight.

[0057] In the present invention, the calculation formula for the content of phosphate in the composite corrosion and scale inhibitor is:

[0058]

[0059] Where, m1—mass of phosphate, g;

[0060] m—sample mass of composite corrosion and scale inhibitor, g.

[0061] As described above, the third aspect of the present application provides a composite corrosion and scale inhibitor prepared by the method of the aforementioned second aspect.

[0062] As described above, the fourth aspect of the present application provides an application of the composite corrosion and scale inhibitor of the aforementioned third aspect in geothermal water corrosion and scale inhibition.

[0063] As described above, the fifth aspect of the present application provides a method for geothermal water corrosion and scale inhibition, which comprises adding the composite corrosion and scale inhibitor of the aforementioned third aspect into geothermal water before the geothermal water is discharged from a well.

[0064] Preferably, the temperature of the geothermal water is >30℃. More preferably, the temperature of the geothermal water is 50-100℃.

[0065] Preferably, the salinity of the geothermal water is 10000-30000 mg / L.

[0066] Preferably, the dissolved oxygen concentration of the geothermal water is >1.0 mg / L, and the dissolved oxygen concentration of the geothermal water is lower than the saturated dissolved oxygen concentration.

[0067] Preferably, the addition amount of the composite corrosion and scale inhibitor is 90-100 mg / L based on the volume of the geothermal water. The inventors have found that in this preferred embodiment, a composite corrosion and scale inhibitor with better corrosion and scale inhibition effect can be obtained.

[0068] The present application will be described in detail below by way of examples.

[0069] In the following examples, the experimental instruments and raw materials involved are commercially available unless otherwise specified.

[0070] Experimental instruments

[0071] Rotary test instrument: SYZL-II, Gao Mei Qin You Chemical Co., Ltd.

[0072] raw material

[0073] Dodecyltriphenylphosphonium chloride: self-made, synthesized according to the method of Example 1 in CN106977546A;

[0074] Tetradecyltriphenylphosphonium chloride: self-made, synthesized according to the method of Example 2 in CN106977546A;

[0075] Hexadecyltriphenylphosphonium chloride: self-made, synthesized according to the method of Example 3 in CN106977546A;

[0076] Tetradecyltributylphosphonium chloride: Aladdin Reagent Co., Ltd.

[0077] Tetrakishydroxymethylphosphonium sulfate: Aladdin Reagent Co., Ltd.

[0078] PESA: Shandong Taihe Water Treatment Technology Co., Ltd.;

[0079] HPMA: Shandong Taihe Water Treatment Technology Co., Ltd.

[0080] PASP: Shandong Taihe Water Treatment Technology Co., Ltd.;

[0081] Sodium gluconate: Tianjin Damao Chemical Reagent Factory;

[0082] Potassium gluconate: Tianjin Damao Chemical Reagent Factory;

[0083] PBTC: Shandong Taihe Water Treatment Technology Co., Ltd.

[0084] HPAA: Shandong Taihe Water Treatment Technology Co., Ltd.;

[0085] NaOH: Tianjin Damao Chemical Reagent Factory;

[0086] KOH: Tianjin Damao Chemical Reagent Factory;

[0087] Anhydrous zinc chloride: Tianjin Damao Chemical Reagent Factory;

[0088] Zinc sulfate: Tianjin Damao Chemical Reagent Factory;

[0089] Zinc nitrate: Tianjin Damao Chemical Reagent Factory.

[0090] The amounts of components in the following examples are expressed in parts by weight. Unless otherwise specified, each part by weight represents 1 g.

[0091] Example 1

[0092] The formula and process parameters of this example are shown in Table 1, and the composite corrosion and scale inhibitor S1 was prepared according to the following method.

[0093] The method for preparing the composite corrosion inhibitor and scale inhibitor comprises the following steps:

[0094] At 25° C., the components of the composite corrosion inhibitor and scale inhibitor composition were placed in a glass container and mixed for 1 hour at a rotation speed of 75 rpm to obtain composite corrosion inhibitor and scale inhibitor S1.

[0095] Unless otherwise specified, the remaining examples were carried out using the same process as Example 1, except that the formulations of the composite corrosion and scale inhibitor compositions and the process parameters used were different, as shown in Table 1.

[0096] Table 1

[0097]

[0098] Table 1 (continued)

[0099]

[0100]

[0101] Test Example 1

[0102] The composite corrosion and scale inhibitors obtained in each example were subjected to performance determination by using the following test methods.

[0103] A dynamic corrosion test was carried out by using a rotating wheel tester to simulate the field conditions, and the addition amount of the composite corrosion and scale inhibitor was 100 mg per liter of geothermal water; the test temperature was 70℃, and the test time was 72 h.

[0104] The calcium hardness and the calcium carbonate scale inhibition rate before and after the test were analyzed according to GB / T 16632-2019 “Determination of the scale inhibition performance of water treatment agents - Calcium carbonate deposition method”.

[0105] The calculation formulas of the corrosion inhibition rate and the calcium carbonate scale inhibition rate are as follows:

[0106]

[0107] In the formula, V0 is the corrosion rate of the test piece without adding the corrosion and scale inhibitor, mm / a;

[0108] V is the corrosion rate of the test piece with adding the corrosion and scale inhibitor, mm / a.

[0109]

[0110] In the formula, p4 is the value of the mass concentration of Ca 2+ (as CaCO3) in the test solution after adding the scale and corrosion inhibitor, mg / L;

[0111] p3 is the value of the mass concentration of Ca 2+ (as CaCO3) in the test solution without adding the scale and corrosion inhibitor, mg / L;

[0112] p is the value of the mass concentration of Ca 2+ (as CaCO3) in the test water, mg / L.

[0113] The test water was geothermal water from a certain area in Henan Province, and the water quality analysis results are shown in Table 2.

[0114] The performance determination results of the composite corrosion and scale inhibitors obtained in each example are shown in Table 3.

[0115] Table 2

[0116] project Numerical pH 6.60 Conductivity / (μS / cm) 20000 <![CDATA[氢氧化物碱度(CaCO3计) / (mg / L)]]> 0.00 <![CDATA[碳酸盐碱度(CaCO3计) / (mg / L)]]> 0.00 <![CDATA[重碳酸盐碱度(CaCO3计) / (mg / L)]]> 83.03 <![CDATA[总硬度(CaCO3计) / (mg / L)]]> 2880.00 <![CDATA[钙硬度(CaCO3计) / (mg / L)]]> 2375.00 <![CDATA[镁硬度(CaCO3计) / (mg / L)]]> 505.00 ρ(Cl - ) / (mg / L)]]> 9911.96 <![CDATA[ρ(SO4 2- ) / (mg / L)]]> 437.38 ρ(total iron) / (mg / L) 13.14 ρ(ammonia nitrogen, N) / (mg / L) 5.63 <![CDATA[ρ(Zn 2+ ) / (mg / L)]]> 0.00 <![CDATA[ρ(可溶性SiO2) / (mg / L)]]> 35.24

[0117] Table 3

[0118] Examples Corrosion inhibition rate / % Calcium carbonate scale inhibition rate / % Example 1 83.2 87.3 Example 2 90.5 86.9 Example 3 92.1 88.6 Example 4 91.7 89.3 Example 5 82.4 88.3 Comparative Example 1 26.41 80.89 Comparative Example 2 42.47 85.61 Comparative Example 3 47.42 85.62 Comparative Example 4 50.23 86.21 Comparative Example 5 54.3 87.6 Comparative Example 6 62.3 87.1

[0119] From the above results, it can be seen that the composite corrosion inhibitor and scale inhibitor provided by the present invention has good corrosion inhibition and scale inhibition effects in geothermal water systems with medium to low temperatures and an oxygen-containing environment.

[0120] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as the contents disclosed by the present invention and fall within the scope of protection of the present invention.

Claims

1. A composite corrosion inhibitor and scale inhibitor composition, characterized in that: The composition contains the following components: phenethyl quaternary phosphonium salt, polymer A, gluconate, organic phosphine compound, inorganic base, water-soluble inorganic zinc salt and water; Relative to 100 parts by weight of the composite corrosion inhibitor and scale inhibitor composition, the content of the phenethyl quaternary phosphonium salt is 10-30 parts by weight, the content of the polymer A is 2-15 parts by weight, the content of the gluconate is 2-12 parts by weight, the content of the organic phosphine compound is 2-8 parts by weight, the content of the inorganic base is 2-13 parts by weight, the content of the water-soluble inorganic zinc salt is 2-12 parts by weight, and the content of water is 10-80 parts by weight; Wherein, the phenethyl quaternary phosphonium salt has a structure shown in formula (1), Formula (1), In formula (1), X is chlorine, and n is 12, 14 or 16; The polymer A is selected from at least one of polyaspartic acid, polyepoxysuccinic acid and hydrolyzed polymaleic anhydride; The organic phosphine compound is 2-hydroxyphosphonoacetic acid and / or 2-phosphono-1,2,4-tricarboxylic acid butane.

2. The composite corrosion inhibitor and scale inhibitor composition according to claim 1, wherein: Relative to 100 parts by weight of the composite corrosion inhibitor and scale inhibitor composition, the content of the phenethyl quaternary phosphonium salt is 12-25 parts by weight, the content of the polymer A is 5-10 parts by weight, the content of the gluconate is 5-10 parts by weight, the content of the organic phosphine compound is 4-6 parts by weight, the content of the inorganic base is 5-10 parts by weight, the content of the water-soluble inorganic zinc salt is 4-9 parts by weight, and the content of water is 30-65 parts by weight.

3. The composite corrosion inhibitor and scale inhibitor composition according to claim 1 or 2, wherein: The gluconate is selected from at least one of sodium gluconate, potassium gluconate, sodium D-gluconate, potassium D-gluconate, zinc gluconate and manganese gluconate.

4. The composite corrosion inhibitor and scale inhibitor composition according to claim 1 or 2, wherein: The inorganic base is selected from at least one of sodium hydroxide and potassium hydroxide.

5. The composite corrosion inhibitor and scale inhibitor composition according to claim 1 or 2, wherein: The water-soluble inorganic zinc salt is selected from at least one of zinc chloride, zinc nitrate and zinc sulfate.

6. A method for preparing a composite corrosion and scale inhibitor, characterized in that: The method comprises: mixing the components of the composite corrosion and scale inhibitor composition according to any one of claims 1 to 5.

7. The method according to claim 6, wherein: The mixing conditions at least meet the following requirements: temperature of 10-30° C., time of 0.5-1 h, and stirring speed of 60-90 rpm.

8. The method according to claim 6, wherein: The amount of each component in the composite corrosion inhibitor and scale inhibitor composition is controlled so that the content of phosphate in the prepared composite corrosion inhibitor and scale inhibitor is less than 2% by weight.

9. A composite corrosion inhibitor and scale inhibitor prepared by the method according to any one of claims 6 to 8.

10. Use of the composite corrosion and scale inhibitor according to claim 9 in geothermal water corrosion and scale inhibition.

11. A method for geothermal water corrosion and scale inhibition, characterized in that: The method comprises: adding the composite corrosion inhibitor and scale inhibitor according to claim 9 into the geothermal water before the geothermal water comes out of the well.

12. The method according to claim 11, wherein The temperature of the geothermal water is greater than 30°C.

13. The method according to claim 12, wherein: The temperature of the geothermal water is 50-100°C.

14. The method according to any one of claims 11 to 13, wherein: The mineralization of the geothermal water is 10,000-30,000 mg / L.

15. The method according to any one of claims 11 to 13, wherein: The dissolved oxygen concentration of the geothermal water is greater than 1.0 mg / L, and the dissolved oxygen concentration of the geothermal water is lower than the saturated dissolved oxygen concentration.

16. The method according to any one of claims 11 to 13, wherein: Based on the volume of the geothermal water, the added amount of the composite corrosion inhibitor and scale inhibitor is 90-100 mg / L.

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