CN1048999C - Filtering-loss reducing agent of humic resin and its prepn - Google Patents

Abstract

A humic acid resin fluid loss reducer used as a drilling mud treatment agent and a preparation method thereof, the fluid loss reducer is composed of a humic acid active intermediate, a water-soluble polyacrylonitrile ammonium salt complex and a water-soluble carbonamide resin , the preparation method is a one-step or two-step process without slagging. It has the advantages of high production intensity, high utilization rate of raw materials, no secondary pollution, good temperature resistance and salt resistance. It is widely used in deep wells polluted by fresh water, salt water and medium salt.

Description

A kind of humic acid resin fluid loss reducer and preparation method thereof

The invention belongs to a drilling fluid treatment agent, in particular to a humic acid resin fluid loss reducer and a preparation method thereof.

In the 1970s, U.S. Patent (US 3,956,140) reported polymer fluid loss control agents synthesized from phenol, urea, formaldehyde, sulfite, and other modified components such as melamine, salicylic acid, benzoic acid, and phthalic acid. However, due to the synthesis method and the condensation process controlled by adding water to the pure polymer, this condensation process is difficult to control, and has disadvantages such as high cost and poor temperature resistance, but it has not been widely used in practice. The Resinex (fluid loss reducer) of Magcobar Company in the United States is a combination of lignite and sulfonated phenolic resin (SMP). This product has better temperature resistance than a purely polymer-synthesized fluid loss reducer, and its cost has also decreased.

In the 1980s, the lignite resin drilling fluid fluid loss control agent developed by our country, such as the Chinese patent "A new type of drilling mud treatment agent containing humic acid and its preparation method" (Patent No. 85106524), the patent is based on sulfomethylated humic acid Sodium bicarbonate, sulfomethyl phenolic resin and sulfomethyl hydrolyzed polyacrylonitrile are used as raw materials, and are obtained through the process route of lignite atmospheric pressure extraction→sedimentation and slagging→evaporation concentration, and then graft polymerization with phenolic resin after sulfonation product. Although its product performance exceeds that of Resinex in the United States, it still has the disadvantages of strictly limited raw material sources, low raw material utilization, high cost and secondary pollution caused by sedimentation and slag discharge.

The purpose of the present invention is to provide a cheap humic acid resin fluid loss reducer and its preparation method which is not limited by the type of raw coal and does not cause secondary pollution.

The humic acid resin fluid loss reducer of the present invention consists of humic acid (HA) active intermediate, water-soluble polyacrylonitrile ammonium salt complex polymer and water-soluble carbonamide resin, and the weight percentage of each component is:

Humic acid (HA) active intermediate 15-70%

Water-soluble polyacrylonitrile ammonium salt complex polymer 5-40%

Water-soluble carbonamide resin 10-50%;

Described humic acid (HA) active intermediate is:

A. Use weathered coal as raw material to be suitable for the humic acid (HA) active intermediate of the fluid loss control agent of salt cement slurry, which is composed of weathered coal, water, strong alkali, and strong humic acid (HA) active intermediate content greater than 35%. Oxidants, sulfides, sulfonating agents and formaldehyde, the content of each component is:

Weathered coal 1 water 2-5 strong oxidant 0.01-0.1

Sulfide 0.005-0.05 Strong base 0.07-0.25 Sulfonating agent 0.03-0.15

Formaldehyde 0-0.25

Wherein the strong base is one or a combination of potassium hydroxide and sodium hydroxide, and the strong oxidizing agent is one or more of alkali metal permanganate, double complex salt, chlorate, hydrogen peroxide, persulfate Several mixtures; the sulfide is one or more mixtures of ferrous sulfate, alkali metal sulfide containing ammonium sulfide, and the sulfonating agent is one or more of sodium sulfite, sodium bisulfite, ammonium sulfite, sodium metabisulfite a mixture;

B. Use weathered coal as raw material to be suitable for the humic acid (HA) active intermediate of the fluid loss control agent of freshwater low-salt mud, which is composed of weathered coal and strong alkali and water with humic acid (HA) content greater than 35%. Part content (weight ratio) is:

Weathered coal 1 water 2-5 strong alkali 0.07-0.20

Wherein strong base is a kind of or its mixture in potassium hydroxide, sodium hydroxide;

C. The active intermediate of humic acid (HA) when taking lignite and peat as raw materials is composed of coal, water, strong alkali, sulfonating agent, and formaldehyde whose content of humic acid (HA) is greater than 35%. )for:

coal 1 water 2-5 strong alkali 0.08-0.25

Sulfonating agent 0.03-0.20 Formaldehyde 0-0.35

The coal can be lignite, peat or their oxygenolysis products, the strong base is one or a combination of potassium hydroxide and sodium hydroxide; the sulfonating agent is sodium sulfite, sodium bisulfite, ammonium sulfite, sodium metabisulfite one or a mixture of several.

The described water-soluble polyacrylonitrile ammonium salt complex polymer consists of water-soluble polyacrylamide ammonium salt, water and additives, and its component content (weight ratio) is:

Water-soluble polyacrylonitrile ammonium salt 1 water 0.1-6 additive 0.05-0.45

The additives can be polyacrylamide (PAM), sulfomethylated polyacrylamide (SPAM), carboxymethyl cellulose, hydroxyethyl cellulose, polyethylene glycol, polyvinyl alcohol, polyoxyethylene phenol ether , one or several mixtures of borax.

Described water-soluble carboxamide resin consists of carboxamides, formaldehyde, sulfonating agent, strong base, water, and its component content (weight ratio) is:

Carbonamides 1 Strong base 0.005-0.03

Formaldehyde 0.5～2.5 Water 0.1～1

Sulfonating agent 0.05～1

Among them, carbonamides can be one or more mixtures of neutral carbonamides, methylol carbonamides, Fe, Al, Zn, Mn, Ti, Zr, Hf complexes and ureides of carbonamides, sulfonated The agent can be one or a mixture of sodium sulfite, sodium bisulfite, ammonium sulfite, sodium metabisulfite; the strong base can be one of sodium hydroxide, potassium hydroxide or a mixture thereof.

The preparation method of the present invention is as follows:

1. Preparation of HA active intermediate

(1) When using weathered coal as raw material to prepare products suitable for brine cement slurry

a. weigh according to the HA active intermediate composition content of above-mentioned A;

b: Add water to weathered coal, and react with strong oxidant at 80-160°C for 0.5-6 hours;

c: After the reaction, add sulfide and react at 80-140°C for 0.5-3 hours;

d: After the reaction, add a strong base, a sulfonating agent, and formaldehyde and react at 100-180° C. for 1-5 hours to obtain an active intermediate of HA.

(2) When weathered coal is used as raw material to prepare products suitable for freshwater low-salt (NaCl≤4%) type mud system products

a: weighed according to the content of the HA active intermediate component of the above-mentioned B;

b: Add water and strong alkali to weathered coal and react at 30-150°C for 0.5-3 hours to obtain the active intermediate of HA.

(3) When lignite and peat are used as raw materials

a: Weighing according to the content of the HA active intermediate component of the above C;

b: Add water and strong alkali to lignite or peat and react at 30-150°C for 0.5-3 hours;

c: After the reaction, add sulfonating agent and formaldehyde and react at 100-160° C. for 0.5-5 hours to obtain the active intermediate of HA.

2. Preparation of water-soluble polyacrylonitrile ammonium salt complex

a. weighed by the above-mentioned water-soluble polyacrylonitrile ammonium salt complex polymer component content;

b: Mix water and additives with water-mediated polyacrylonitrile ammonium salt, and react at 20-100°C for 0.2-2 hours.

3. Preparation of Water-Soluble Carboamide Resin

a. Weigh by the component content of above-mentioned water-soluble carbonamide resin;

b. Mix the components and react at 50-150°C for 0.5-4 minutes;

(4) Synthetic fluid loss additive

(1) a. the product that 1,2,3 step makes is weighed by described humic acid resin fluid loss reducer composition content;

b. Add the products obtained in steps 1, 2, and 3 to the reactor at the same time, react at a temperature of 100-160°C for 16 hours, and then evaporate the water to obtain a solid product;

(2) a. According to the component content of the humic acid resin class fluid loss reducer, the product obtained in steps 2 and 3 is weighed according to the component content of the water-soluble carbonamide resin;

b. Add the required components prepared in steps 2 and 3 to the intermediate prepared in 1 at the same time, react at 100-160°C for 1-6 hours, and evaporate the water to obtain a solid product.

The Humic Acid Resin Fluid Loss Reducer of the present invention is made into a base slurry containing 7% bentonite by the mud station of the No. 3 Drilling Engineering Company of Huabei Oilfield and the No. 1 Drilling Company of Daqing Oilfield. PV YP Static shear force API dehydration High temperature and high pressure dehydration

(Lmin) (w/v) 100 ℃/h (mpa.s) (mpa.s) (PA) (PA) (PA) ml ml ml/30min × 2 freshwater plasma*R, T 29.5 3 26.5 10 25-

180/16 → RT 35 5 30 25SCur R, T 22 18 4 0 9.2 -3 % Freshwater 180/16 → RT 15 3 0 8.5 24SCur 5 % R, T 27 13, 25 8-10 % NaCl 180/16 → RT 19 10 6 6 12 32SCur 5 % R, T 25.5 8.5 18 8.5 -15 % NaCl 180/16 → RT 16 7 7 7 12.5 35

*R, T—room temperature; AV—apparent viscosity; YP—dynamic shear force;

PV—plastic viscosity; SCUR—is the code name of the fluid loss reducer of the present invention.

The advantages of the humic acid resin fluid loss reducer of the present invention are as follows:

1. Adopt non-slag discharge process, high production intensity, high utilization rate of raw materials, no secondary pollution, low cost and good benefit;

2. Good resistance to high temperature and salt immersion;

3. Reduce fluid loss without increasing viscosity, and improve rheology;

4. The quality of the formed mud cake is dense and smooth, and the well diameter is regular, which is beneficial to protect the wellbore and stabilize the well wall;

5. Widely applicable to deep wells polluted by fresh water, salt water, and medium salt (10-15% sodium chloride);

6. It has good compatibility and can be used as a composite agent with other treatment agents to improve the effect and reduce the comprehensive cost of drilling.

Embodiments of the present invention are as follows:

Example 1

(1) Add 10g of weathered coal, 0.15g of KMnO ₄ , 30g of water into the reactor, react at 80°C for 0.5 hours, add 0.1g of Na ₂ S and continue the reaction for 0.5 hours, add 0.8g of NaOH, 0.25g of Na ₂ SO ₃ , NaHSO ₃ 0.2g, 1.2g formaldehyde, and sulfonation temperature 130°C for 1.2 hours to obtain the active intermediate of HA.

(2) Add 4.5g of water-mediated polyacrylonitrile ammonium salt, 14g of water, 0.2g of SPAM (sulfomethylated polyacrylamide) and 0.22g of carboxymethyl cellulose to react at 20-30°C for 0.5 hours, A water-soluble polyacrylonitrile ammonium salt complex is obtained.

(3) Add 2.6 g of carboxamide, 0.2 g of NaHSO ₃ , 3 g of formaldehyde, 0.03 g of NaOH, and 3.5 g of water into the reactor, and react at 70° C. for 1.2 hours to obtain a water-soluble carboxamide resin.

(4) Put the above-mentioned intermediate materials (1), (2) and (3) into the reactor at one time, mix them at 130°C for 4 hours, and then evaporate to dryness to obtain a solid product.

Example 2

Change the KMnO ₄ in (1) in Example 1 to 0.3g, react at 150°C for 2 hours, change Na ₂ S to 0.07g and react at 100°C for 0.5 hour, change the sulfonation temperature to 140°C, and the rest are the same as Example 1.

The polyacrylonitrile ammonium salt of (2) in example 1 is changed into 2.5g, and additive SPAM is changed into PAM 0.2g, and all the other are the same as example 1.

The preparation of (3) in Example 1 is the same as Example 1.

The reaction condition of (4) among the example 1 is changed into 100 ℃, 5 hours reaction, all the other are the same as example 1.

Example 3

Change the NaOH prepared in (1) in Example 1 to 1.5g, Na ₂ SO ₃ to 0.4g, NaHSO _{3 to} 0.3g, formaldehyde to 1.7g, and the sulfonation reaction to 135°C for 2 hours and the rest to be the same as Example 1.

The hydrolyzed polyacrylonitrile ammonium salt complex was prepared according to the conditions of (2) in Example 1.

Water-soluble carboxamide resin was prepared according to the conditions of (3) in Example 1.

The reaction temperature of (4) in example 1 was changed to 140 ℃ for 3.5 hours, and all the other were the same as example 2.

Example 4

(1) Add 10g of weathered coal, 40g of water, 0.2g of strong oxidant KMnO ₄ and 0.01g of Na ₂ Cr ₂ O ₇ .2H ₂ O to the reactor, react at 160°C for 1.5 hours, then add 0.13g of Na ₂ S and react at 120°C 0.5 hours. Add 1.8g of NaOH, 0.5g of sodium metabisulfite, and 0.85g of formaldehyde and react at 145°C for 3 hours to obtain the active intermediate of HA.

(2) Add 2 g of water-mediated polyacrylonitrile ammonium salt, 9 g of water, 0.17 g of additives PAM, 0.06 g of borax, and 0.15 g of polyoxyethylene phenol ether into the reactor, and react at 50° C. for 40 minutes to obtain a compound of hydrolyzed polyacrylonitrile amine salt. Polymer.

(3) Add 3.75g of methylol carboxamide, 2g of sodium metabisulfite, 8.5g of formaldehyde, 0.1g of NaOH, 1.2g of water in the reactor, and react at 120° C. for 1 hour and 10 minutes to obtain a water-soluble carboxamide resin.

(4) Put the above-mentioned intermediate materials (1), (2) and (3) into the reactor at one time and mix them, react at 150° C. for 6 hours, and then evaporate the water to obtain a solid product.

Example 5

Change the strong oxidant in (1) in Example 4 to 0.3g of ammonium persulfate, react at 130°C for 2.5 hours, then change Na ₂ S to FeSO ₄ .7H ₂ O 0.5g, react at 110°C for 50 minutes, and then add NaOH The rest of 1.4g is the same as Example 4.

The preparation additive of (2) among the example 4 is changed into carboxymethylcellulose 0.25g, Polyethylene Glycol 0.1g, reacted at 40 ℃ 20 minutes, all the other are the same as Example 4.

The preparation of methylol carbonamide in (3) in example 4 is changed to carbonamide manganese complex 4g and all the other are the same as example 4.

The synthetic reaction condition of (4) in example 4 is 160 ℃ 2 hours, all the other are with example 4.

Example 6

Change (1) oxidant in Example 4 to H ₂ O ₂ 1g, and the rest are the same as Example 4.

In Example 4 (2), the hydrolyzed polyacrylonitrile ammonium salt was changed to 1.5 g, and the additives were changed to 0.3 g of polyvinyl alcohol and 0.2 g of hydroxyethyl cellulose, and the rest were the same as in Example 4.

(3) is prepared with example 4.

The synthetic condition of (4) changed 120 DEG C 4 hours all the other with example 4.

Example 7

The oxidizing agent in (1) in Example 4 was changed to 0.25g of potassium chlorate and 0.1g of KMnO ₄ , the reaction conditions were changed to 130°C for 3 hours, and then 0.14g of Na ₂ S was added. The reaction conditions were 125°C and the reaction was performed for 1 hour.

In example 4, the additive of (2) is changed into polyoxyethylene phenol ether 0.2g, carboxymethyl cellulose 0.5g, all the other are the same as example 4, make water-mediated polyacrylonitrile ammonium salt complex polymer.

In Example 4, the carboxamide in (3) was changed to 2.8 g of acyl urea, the sulfonating agent was changed to 2.5 g of NH ₄ SO ₃ , the reaction was changed to 150° C. for 0.5 hour, and the rest were the same as in Example 4.

The synthetic reaction condition of (4) in example 4 is changed to 145 ℃ 4.5 hours all the other are the same as example 4.

Example 8

After obtaining the HA active intermediate according to the preparation conditions in (1) in Example 3, weigh each component material according to the material composition in the preparation of (2) and (3) in Example 4 and then add the intermediate obtained by (1) at one time. After reaction at 140°C for 4 hours, the water was evaporated to obtain a solid product.

Example 9

(1) Add weathered coal 10g, water 50g, KMnO ₄ 0.5g into the reactor, add Na ₂ S 0.18g after reacting at 125°C for 2 hours, add NaOH 1.6g, sodium metabisulfite 0.45 after reacting at 90°C for 20 minutes g, formaldehyde 0.75g, sulfomethylated at 150°C for 3 hours to obtain the active intermediate of HA.

(2) weigh each component material according to the material composition of (2) preparing water-mediated polyacrylonitrile ammonium salt complex polymer in example 7, weigh each component according to the material composition of preparing (3) in example 4, disposable Add the active intermediate of HA obtained from (1), and react at 135°C for 5.5 hours to evaporate the water to obtain the product.

Example 10

The sodium metabisulfite of (1) is changed into 1.3g among the example 9, and formaldehyde is 2.3g, and all the other step conditions are the same as example 9.

Example 11

(1) Add 10g of weathered coal, 0.12g of KClO ₃ , 32g of water to the reactor, react at 120°C for 2 hours, add 0.04g of Na ₂ S, FeSO ₄ .7H ₂ O 0.01g, react at 100°C for 0.5 hours, add KOH 2g , HaHSO ₃ 0.3g, sodium metabisulfite 0.3g, formaldehyde 1.5g, react at 180°C for 1 hour and 10 minutes to obtain the active intermediate of HA.

(2) Add 1.5g of hydropolyacrylonitrile ammonium salt, 0.2g of SPAM, 0.15g of borax, 2.5g of carbonamide, 1.7g of sodium metabisulfite, 4g of formaldehyde into the reactor containing the HA active intermediate, and react at 115°C for 6 hours , evaporated to obtain a solid product.

Example 12

Just when (3) in example 4 is prepared water-soluble carbonamide resin, change methylol carbonamide into the methylol carbonamide complex 3.6g containing 1% Fe or Al or Mn or Ti, its preparation method is Add the corresponding salt whose metal ion content is 1% calculated according to the corresponding metal salt (sulphate or chloride) to the aqueous solution of 20-40% of methylol carbonamide, and react at 50-80°C for 0.5 hours to obtain the corresponding complex , evaporate water to obtain solid carbonamide complex, and all the other steps are the same as Example 4.

Example 13

In Example 12, the methylol carbonamide complex is changed to a complex containing 2% Mn or Fe or Zn or Ti, and the complex amount is 3.2g. The preparation method is the same as Example 12, and all the other steps are the same as Example 12.

Example 14

(1) Add 20g of weathered coal, 80g of water, and 3g of NaOH to the reactor and react at 80°C for 1 hour to prepare the active intermediate of HA.

(2) Add 7 g of water-mediated polyacrylonitrile ammonium salt, 7 g of water, and 0.35 g of carboxymethyl cellulose into the reactor, and react at 30° C. for 0.5 hour to obtain a water-mediated polyacrylonitrile ammonium salt complex.

(3) Add 3 g of carbonamide, 3 g of water, 1 g of NaHSO ₃ , 2 g of sodium metabisulfite, 0.05 g of NaOH, and 5.8 g of formaldehyde into the reactor, and react at 90° C. for 2 hours to obtain a water-soluble carbonamide resin.

(4) In the reactor, put the intermediates obtained in (1), (2) and (3) into the reactor at one time, react at 100° C. for 4.5 hours, and evaporate the water to obtain a solid product.

Example 15

(1) Add 15g of weathered coal, 45g of water, and 1.8g of KOH to the reactor and react at 100°C for 40 minutes to obtain the active intermediate of HA. Then weigh the components in (2) and (3) according to Example 14, and then add the HA active intermediate obtained from (1) at one time. The synthesis temperature is 130 ° C. After 3 hours of reaction, the water is evaporated to obtain a solid. product.

Example 16

The reaction conditions in (1) in Example 15 were changed to 30° C., and the reaction conditions were the same as Example 15 for 1 hour.

Example 17

In Example 16, the synthesis temperature was changed to 140° C. for 4 hours, and other conditions were the same as Example 16.

Example 18

In example 16, the temperature of (1) was changed to 120° C., and the reaction time was 45 minutes, and the remaining examples 16.

Example 19

(1) Add 10g of weathered coal, 30g of water, and 1.35g of NaOH to the reactor at 70°C for 1 hour to obtain the active intermediate of HA.

(2) Add 3 g of methylol carbonamide, 1.2 g of sodium bisulfite, 4 g of formaldehyde, 0.8 g of water-mediated polyacrylonitrile ammonium salt, 0.22 g of PAM, and 0.22 g of polyoxyethylene into the reactor containing the active intermediate of HA. 0.1 g of phenol ether was reacted at 150° C. for 3 hours, and then the water was evaporated to obtain a solid product.

Example 20

(1) Prepare the active intermediate of HA according to the conditions of (1) in Example 19.

(2) According to Example 4 (2), a water-mediated polyacrylonitrile ammonium salt complex was prepared.

(3) Prepare water-soluble carboxamide resin according to example 12(3).

(4) Mix (1), (2) and (3) in a reactor once at 120° C., react for 3 hours and distill off the water to obtain a solid product.

Example 21

(1) Prepare the active intermediate of HA according to the conditions of (1) in Example 19.

(2) According to the conditions of (2) in Example 7, a water-mediated polyacrylonitrile ammonium salt complex was prepared.

(3) Prepare water-soluble carboxamide resin according to the conditions of (3) in Example 13.

(4) Mix (1), (2), and (3) intermediates in a reactor at one time and react at 110° C. for 8 hours to form a product, and evaporate the water to obtain a solid product.

Example 22

(1) Add 15g of weathered coal, 50ml of water, 0.5g of NaOH, 2g of KOH into the reactor and react at 35°C for 50 minutes to obtain the active intermediate of HA.

(2) Add 5 g of water-mediated polyacrylonitrile amine salt, 10 ml of water, 0.12 g of polyvinyl alcohol, 0.1 g of polyethylene glycol, and 0.05 g of borax to the reactor, and react at 40°C for 40 minutes to obtain a water-mediated polyacrylonitrile ammonium salt complex .

(3) Add 8.5 g of acyl urea, 2.5 g of water, 1 g of NH ₄ SO ₃ , 1.5 g of sodium metabisulfite, 0.03 g of NaOH, and 25.5 g of formaldehyde in the reactor, and react at 120° C. for 0.5 hour to obtain a water-soluble carboxamide resin.

(4) The intermediates of (1), (2) and (3) were mixed in a reactor at 145° C., reacted for 2.5 hours, and evaporated to obtain a solid product.

Example 23

(1) lignite 10g, water 40g, NaOH 1.4g, react at 80°C for 1 hour and 10 minutes, add sodium metabisulfite 0.8g, formaldehyde 1.5g, react at 130°C for 2 hours to obtain HA active intermediate.

(2) Add 3g of hydrolyzed polyacrylonitrile ammonium salt, 3g of water, 0.1g of PAM (polyacrylamide), 0.12g of carboxymethyl cellulose into the reactor, and react at 25°C for 0.5 hours to obtain a water-mediated polyacrylonitrile ammonium salt complex polymer .

(3) Add 2 g of carbonamide, 1.2 g of sodium metabisulfite, 2 g of water, 3.2 g of formaldehyde, and 0.01 g of NaOH in the reactor and react at 60°C for 1 hour and 20 minutes to obtain a water-soluble carbonamide resin.

(4) Mix (1), (2), and (3) intermediates in a reactor at 120°C at one time, react for 4 hours, and distill off the water to obtain a solid product.

Example 24

(1) Prepare the active intermediate of HA according to the conditions of Example 23(1).

(2) Add 2g of hydrolyzed polyacrylonitrile ammonium salt, 7g of water, 0.15g of SPAM (sulfonated polyacrylamide), 0.12g of polyoxyethylene phenol ether, and 0.05g of borax to the reactor, and react at 30°C for 40 minutes to obtain hydrolyzed polypropylene Nitrile ammonium compound.

(3) 3.6g methylol carboxamide in the reactor, 0.8 sodium metabisulfite, 0.5g sodium sulfite, 0.4g ammonium sulfite, NaOH 0.07g, water 3g, formaldehyde 4g, 100 ℃ of reactions obtained water-soluble carboxamide resin in 40 minutes.

(4) The intermediate products obtained in (1), (2) and (3) were mixed in a reactor at one time and reacted at 100° C. for 6 hours, and then the water was evaporated to obtain a solid product.

Example 25

(1) lignite 10g, water 35g, NaOH 2g, react at 30°C for 0.5 hours, add sodium bisulfite 0.8g, sodium sulfite 1.1g, react at 150°C for 1 hour and 40 minutes to obtain HA active intermediate.

(2) prepare water-soluble polyacrylonitrile ammonium salt complex polymer and water-soluble carbonamide resin respectively by (2), (3) in example 24, then they are mixed with the HA intermediate obtained by (1) in the reactor Mix within one time, react at 140°C for 3 hours, and then distill off the water to obtain a solid product.

Example 26

Prepare the active intermediate of HA according to the conditions of (1) in Example 25, then add 1.4g of hydrolyzed polyacrylonitrile ammonium salt, PAM 0.3g, carboxymethylcellulose 0.23g, polyethylene glycol 0.1g, carbon Amide 2.7g, ammonium sulfite 0.2g, sodium metabisulfite 1.3g, formaldehyde 2.8g, reacted at 115°C for 4.5 hours, evaporated to obtain a solid product.

Example 27

(1) In the preparation of Example 25 (1), 2.5 g of formaldehyde was added during sulfonation, and all the other were the same as the conditions of Example 25 (1).

(2) Add 2.5 g of hydrolyzed polyacrylonitrile ammonium salt, 10 g of water, 0.2 g of PAM, and 0.15 g of hydroxyethyl cellulose into the reactor, and react at 50° C. for 0.5 hour to obtain a hydrolyzed polyacrylonitrile ammonium salt complex.

(3) Add 3.5 g of acyl urea, 2.5 g of water, 1 g of ammonium sulfite, 1.8 g of sodium bisulfite, 3.8 g of formaldehyde, and 0.1 g of NaOH in the reactor, and react at 145° C. for 30 minutes to obtain a water-soluble carbonamide resin.

(4) Mix the intermediates obtained in (1), (2) and (3) in a reactor once, react at 110° C. for 5 hours, and evaporate the water to obtain a solid product.

Example 28

Change the lignite of (1) into peat 10g in example 23, and all the other conditions are the same as example 23.

Example 29

Change the lignite in example 27 into peat 10g, and all the other conditions are the same as example 26.

Example 30

(1) lignite 10g, water 35g, NaOH 1.7g, react at 120°C for 1.2 hours, add sodium metabisulfite 0.5g, formaldehyde 2.5g, react at 120°C for 0.5 hour to obtain HA active intermediate.

(2) weigh each component according to the composition and content of (2) preparing polyacrylonitrile ammonium salt complex polymer in example 23, and weigh each component according to the composition and content of water-soluble carbonamide resin prepared by (3) in example 27 Add it to the HA intermediate obtained from (1) at one time, react at 145° C. for 3.5 hours, and evaporate the water to obtain a solid product.

Claims (3)

1. A humic acid resin fluid loss reducer is characterized in that it consists of a humic acid (HA) active intermediate, a water-soluble polyacrylonitrile ammonium salt complex polymer and a water-soluble carbonamide resin, each component weight percent The content is: HA active intermediate 15～70% Water-soluble polyacrylonitrile ammonium salt complex 5～40% Water-soluble carbonamide resin 10-50%; The humic acid active intermediate is composed of weathered coal with a humic acid content greater than 35%, water and strong alkali, and is used to prepare fresh water slurry fluid loss reducer, and its component content (weight ratio) is: Weathered coal 1 water 2-5 strong alkali 0.07-0.2; The weight percent of each component of the water-soluble polyacrylonitrile ammonium salt complex is: Water 0.1-6 Hydrolyzed polyacrylonitrile ammonium salt 1 One or more mixtures of polyacrylamide, sulfomethylated polyacrylamide, carboxymethyl cellulose, hydroxyethyl cellulose, polyethylene glycol, polyvinyl alcohol, polyoxyethylene phenol ether, borax 0.05- 0.45; Each component weight ratio of described water-soluble carbonamide resin is: Water 0.1-1 Formaldehyde 0.5-2.5 Strong base 0.005-0.03; One or more mixtures of neutral carbonamide, hydroxymethylcarbonamide, complexes of Fe, Al, Zn, Mn, Ti, Zr, Hf of carbonamide or ureide 1 One or more mixtures of sodium sulfite, sodium bisulfite, ammonium sulfite, sodium metabisulfite 0.05-1. 2. A humic acid resin fluid loss reducer according to claim 1, characterized in that said strong base is one of KOH and NaOH or a mixture thereof. 3. the preparation method of a kind of humic acid resin fluid loss reducer according to claim 1, is characterized in that concrete steps are as follows: (1) Preparation of humic acid (HA) active intermediate When using weathered coal as raw material to prepare products suitable for NaCl≤4% fresh water low-salt mud system a. Weighing according to the active intermediate component content of humic acid (HA); b. Add water to weathered coal, and react with strong alkali at 30-150°C for 0.5-3 hours to obtain humic acid (HA) active intermediate; (2) Preparation of water-soluble polyacrylonitrile ammonium salt complex a. Weighing according to the component content of the water-soluble polyacrylonitrile ammonium salt complex; b. Mix water with one of polyacrylamide, sulfomethylated polyacrylamide, carboxymethyl cellulose, hydroxyethyl cellulose, polyethylene glycol, polyvinyl alcohol, polyoxyethylene phenol ether, borax or Several mixtures are mixed with water-mediated polyacrylonitrile ammonium salt and reacted at 20-100°C for 0.2-2 hours; (3) Preparation of water-soluble carbonamide resin A. weigh by the composition content of described water-soluble carbonamide resin; b. Mix the various components and react at a temperature of 50-150°C for 0.5-4 hours; (4) Synthetic fluid loss additive ①a. The product obtained in steps (1), (2), and (3) is composed of the humic acid resin fluid loss control agent content weighing; b. Add the products obtained in steps (1), (2) and (3) into the reactor at the same time, After 1-6 hours of reaction at high temperature, the water is evaporated to obtain a solid product. ②a. According to the component content of humic acid resin fluid loss control agent, the steps of composition (2) and (3) are obtained The components of the product are weighed according to the above-mentioned component content; b. Add (2), (3) steps to prepare the required components in the intermediate prepared by (1) at the same time After reacting at 100-160°C for 1-6 hours, the water is evaporated to obtain a solid product.