A method for preparing a rubber composite material

Abstract

The present invention belongs to the technical field of rubber materials, and particularly relates to a preparation method of a rubber composite material. Innovatively starting from the front end of gasification fine slag - gasification black water feed liquid, the present invention directly conducts functional modification on it as a raw material liquid; then, the functionalized raw material liquid and rubber emulsion are used to prepare a powder rubber material through emulsion co - coagulation method. This method makes full use of the water in the gasification black water feed liquid, avoids the centrifugal dehydration and direct drying of gasification fine slag, combines the functional treatment of gasification fine slag and the preparation of powder rubber, and has the advantages of short process flow, low production energy consumption, water saving and environmental protection.

Description

Technical Field

[0001] The present invention belongs to the technical field of rubber materials, and particularly relates to a preparation method of a rubber composite material. Background Art

[0002] China is a large country with rich coal resources, and its coal output accounts for more than 50% of the global total output. Coal occupies a dominant position in China's energy composition. With the accelerating transformation of China's energy consumption structure towards clean and low-carbon, the clean and efficient utilization of coal has become an inevitable trend. At present, coal gasification has become one of the key development directions for the clean and efficient utilization of coal, meeting the requirements of the green, low-carbon and high-quality development of China's industry.

[0003] During the coal gasification process, most of the carbonaceous components in coal turn into gas, while the associated inorganic minerals, ungasifiable carbonaceous substances, catalysts, etc. in raw coal are discharged in the form of residues, namely coal gasification slag. Research and analysis results show that about 15 - 20% of the components in coal will be converted into gasification slag during the gasification process. At present, the comprehensive utilization rate of coal gasification ash slag is low, and it is still mainly landfilled and stacked in the open air. The long-term storage of a large amount of gasification ash slag pollutes the soil / water system and the atmospheric environment, seriously threatening the safety of the ecological environment. The comprehensive treatment of coal gasification ash slag has become an outstanding bottleneck restricting the green, low-carbon and sustainable development of the coal chemical industry. At present, the comprehensive utilization of coal gasification slag mainly targets coal gasification fine slag, and the applied research mainly focuses on fields such as carbon component recovery, building materials, soil improvement and water pollution treatment. However, no large-scale, systematic and mature industrial utilization cases for fully consuming coal gasification slag in all components have been seen.

[0004] During the coal gasification process, components such as minerals in coal turn into molten slag. Part of the molten slag is carried out by the gas flow, enters the subsequent purification process, and finally enters the ash water treatment system with the black water discharge to form coal gasification black water flocculant liquid. After being pumped, the black water flocculant liquid is dehydrated to form fine slag with a relatively small particle size, called coal gasification fine slag. Coal gasification fine slag has characteristics such as high water content, mixing of residual carbon and inorganic components, large composition fluctuations and difficult dehydration; at the same time, the carbon and ash components restrict each other, hindering its resource utilization. The carbonaceous component and inorganic silicon-aluminum glassy component in coal gasification fine slag are a typical carbon-silicon hybrid material, with properties such as stable physical and chemical properties, suitable specific surface area and high temperature resistance. After appropriate treatment, it can be used as a compound filler for polymer composites.

[0005] The prior art discloses a method for preparing rubber filler from coal gasification slag, which prepares rubber filler powder through processes such as drying, magnetic separation, activation, ultrafine processing, and surface modification of coal gasification fine slag; the prior art also discloses a rubber filler made from coal gasification fine slag, its preparation method and uses, which removes residual carbon in the coal gasification fine slag and dissolves metal oxides by acid dissolution to obtain mesoporous silica filler; the prior art also discloses a preparation method of a rubber-plastic filler, the rubber-plastic filler and its uses, which makes a slurry of coal gasification fine slag and then collects silicon-rich composite slurry by gravity cyclone, and then performs solid-liquid separation and drying treatment to obtain the rubber-plastic filler.

[0006] In the prior art, coal gasification fine slag samples are collected from coal gasification fine slag yards, and the coal gasification fine slag is processed through a series of processes. The process flow from coal gasification fine slag to polymer composite products is long and complicated; acid treatment is required during the processing of gasification fine slag, which easily produces acid-containing wastewater and causes environmental pollution; drying treatment of coal gasification fine slag is required during the processing. Due to the characteristics of high water content and difficult dehydration of coal gasification fine slag, the production energy consumption is relatively high; at the same time, the existing processes all prepare coal gasification fine slag into filler powder, and the filler powder still needs to be reprocessed with raw rubber, and the functional treatment of coal gasification fine slag and the preparation of rubber materials cannot be organically combined, resulting in a long and complicated application process flow of coal gasification fine slag in rubber-plastic composites.

[0007] Therefore, there is an urgent need for a treatment technology with a short process flow, water-saving, environmental protection and low energy consumption. Summary of the Invention

[0008] Based on the carbon-inorganic component silicon composite structure in coal gasification black water flocculant, the purpose of the present invention is to provide a method for preparing rubber composites using the carbon-inorganic components in coal gasification black water flocculant. The method provided by the present invention has a short process flow, is water-saving, environmentally friendly and has low energy consumption.

[0009] In order to achieve the above purpose, the present invention provides the following technical solutions:

[0010] The present invention provides a method for preparing a rubber composite, comprising the following steps:

[0011] Mix the concentrated liquid obtained by concentrating the coal gasification black water flocculant with a dispersant, and perform grinding and magnetic separation in sequence to obtain a magnetically separated suspension;

[0012] Adjust the magnetically separated suspension to be alkaline, and then perform aging and sieving treatments in sequence to obtain a refined slurry;

[0013] Mix the refined slurry, rubber emulsion and flocculant, and perform flocculation copolymerization to obtain the rubber composite.

[0014] Preferably, the mass concentration of the concentrated liquid is 15-45%;

[0015] The dispersant includes one or more of sodium polyacrylate, sodium stearate, sodium hexametaphosphate, sodium tripolyphosphate, and sodium citrate;

[0016] The mass of the dispersant is 0.3-5.5% of the dry matrix mass of the concentrated liquid.

[0017] Preferably, the time of abrasion is 10-120 min.

[0018] Preferably, the intensity of magnetic separation is 800-1600 Gauss, and the time of magnetic separation is 1-3 min.

[0019] Preferably, the pH value of the alkali is 8.5-11.0;

[0020] The aging temperature is 35-65 °C; the aging is carried out under stirring, and the stirring time is 0.5-1.5 h.

[0021] Preferably, the particle size D90 of the solid particles in the refined slurry is 2-18 μm.

[0022] Preferably, the rubber latex includes one or more of styrene-butadiene rubber latex, natural rubber latex, and nitrile rubber latex;

[0023] The mass concentration of the rubber latex is 40-69%;

[0024] The mass ratio of the dry matrix of the refined slurry to the solid in the rubber latex is 1:1.5-10.

[0025] Preferably, the flocculant includes one or more of MgCl2, Mg(NO3)2, H2SO4, Mg(CH3COO)2, Al2(SO4)3, and KAl(SO4)2;

[0026] The flocculant is mixed in the form of a flocculant solution, and the mass concentration of the flocculant solution is 15-20%.

[0027] Preferably, the temperature of flocculation copolymerization is 35-70 °C, and the flocculation copolymerization is carried out under stirring.

[0028] Preferably, after the flocculation copolymerization, the obtained material is further subjected to mixing and vulcanization in sequence.

[0029] The present invention provides a method for preparing a rubber composite material, comprising the following steps: mixing a concentrated liquid obtained by concentrating a coal gasification black water flocculant liquid with a dispersant, and successively performing grinding and magnetic separation to obtain a suspension after magnetic separation; adjusting the suspension after magnetic separation to be alkaline, and then successively performing aging and sieving treatments to obtain a refined slurry; mixing the refined slurry, a rubber emulsion, and a flocculant, and performing flocculation copolymerization to obtain the rubber composite material.

[0030] Innovatively starting from the front end of coal gasification fine slag - coal gasification black water feed liquid, the present invention directly performs functional modification on it as a raw material liquid; then, the functionalized raw material liquid and the rubber emulsion are used to prepare a powdered rubber material through emulsion co - coagulation method. This method makes full use of the water in the coal gasification black water feed liquid, avoids centrifugal dehydration and direct drying of coal gasification fine slag, combines the functionalization treatment of coal gasification fine slag with the preparation of powdered rubber, and has the advantages of short process flow, low production energy consumption, water saving and environmental protection. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 is a process schematic diagram of the preparation method provided by the present invention;

[0032] Figure 2 is a particle size distribution diagram of the original coal gasification black water flocculant liquid;

[0033] Figure 3 is a particle size distribution diagram of the coal gasification black water concentrated liquid after grinding obtained in Example 1;

[0034] Figure 4 is a particle size distribution diagram of the coal gasification black water concentrated liquid after grinding obtained in Example 2;

[0035] Figure 5 is a particle size distribution diagram of the coal gasification black water concentrated liquid after grinding obtained in Example 3;

[0036] Figure 6 is a particle size distribution diagram of the coal gasification black water concentrated liquid after grinding obtained in Example 4;

[0037] Figure 7 is a particle size distribution diagram of the coal gasification black water concentrated liquid after grinding obtained in Example 5;

[0038] Figure 8 is a particle size distribution diagram of the coal gasification black water concentrated liquid after grinding obtained in Example 6;

[0039] Figure 9 is a particle size distribution diagram of the coal gasification black water concentrated liquid after grinding obtained in Comparative Example 1;

[0040] Figure 10 is a particle size distribution diagram of the coal gasification black water concentrated liquid after grinding obtained in Comparative Example 2;

[0041] Figure 11 The particle size distribution diagram of the coal gasification black water concentrated liquid after abrasion obtained in Comparative Example 3;

[0042] Figure 12 The physical picture of the rubber composite powder obtained in Example 6;

[0043] Figure 13 The physical picture of the rubber composite material obtained in Example 6;

[0044] Figure 14 The SEM image of the rubber composite material obtained in Example 6;

[0045] Figure 15 The TEM image of the rubber composite material obtained in Example 6;

[0046] Figure 16 The SEM image of the rubber composite powder obtained in Comparative Example 1. Detailed implementation manners

[0047] The present invention provides a preparation method of a rubber composite material, comprising the following steps:

[0048] Mix the concentrated liquid obtained by concentrating the coal gasification black water flocculant liquid with a dispersant, and successively perform abrasion and magnetic separation to obtain a magnetically separated suspension;

[0049] Adjust the magnetically separated suspension to be alkaline, and then successively perform aging and sieving treatments to obtain a refined slurry;

[0050] Mix the refined slurry, a rubber emulsion and a flocculant, and perform flocculation copolymerization to obtain the rubber composite material.

[0051] The present invention mixes the concentrated liquid obtained by concentrating the coal gasification black water flocculant liquid with a dispersant, and successively performs abrasion and magnetic separation to obtain a magnetically separated suspension.

[0052] In the present invention, the mass concentration of the concentrated liquid is preferably 15-45%. In the present invention, the concentration process preferably includes: successively subjecting the coal gasification black water flocculant liquid to homogenization dispersion and sedimentation concentration. In the present invention, the mass concentration of the coal gasification black water flocculant liquid is preferably 5-10%. The present invention has no special limitation on the source of the coal gasification black water flocculant liquid, and those well-known to those skilled in the art can be used. The present invention has no special limitation on the processes of homogenization dispersion and sedimentation concentration, and those well-known to those skilled in the art can be used.

[0053] In the present invention, the dispersant preferably comprises one or more of sodium polyacrylate, sodium stearate, sodium hexametaphosphate, sodium tripolyphosphate, and sodium citrate; the mass of the dispersant is preferably 0.3 to 5.5% of the dry matrix mass of the concentrated solution. In the present invention, the mixing is preferably carried out under stirring conditions, and the stirring time is preferably 20 to 30 min.

[0054] In the present invention, the grinding time is preferably 10 to 120 min, more preferably 30 to 90 min. In the present invention, the grinding is preferably carried out in a wet vertical stirring mill. In the present invention, after the grinding, the particle size D90 of the solid particles in the obtained slurry is preferably 5 to 18 μm, and D50 is preferably 2 to 6 μm.

[0055] In the present invention, the magnetic separation intensity is preferably 800 to 1600 Gauss, more preferably 1000 to 1200 Gauss, and the magnetic separation time is preferably 1 to 3 min. In the present invention, the magnetic separation is preferably carried out in a high-gradient magnetic separator.

[0056] After obtaining the magnetically separated suspension, the present invention adjusts the magnetically separated suspension to be alkaline, and then performs aging and sieving treatments in sequence to obtain a refined slurry.

[0057] In the present invention, the pH value of the alkalinity is preferably 8.5 to 11.0, more preferably 9 to 10. The present invention has no special limitation on the adjustment process, and those well-known to those skilled in the art can be used.

[0058] In the present invention, the aging temperature is preferably 35 to 65 °C; the aging is preferably carried out under stirring conditions, and the stirring time is preferably 0.5 to 1.5 h.

[0059] The present invention has no special limitation on the sieving process, and those well-known to those skilled in the art can be used. In the present invention, the particle size D90 of the solid particles in the refined slurry is preferably 2 to 18 μm. In the present invention, the mass concentration of the refined slurry is preferably 20 to 35%.

[0060] After obtaining the refined slurry, the present invention mixes the refined slurry, rubber latex, and flocculant, and performs flocculation copolymerization to obtain the rubber composite material.

[0061] In the present invention, the rubber latex preferably comprises one or more of styrene-butadiene rubber latex, natural rubber latex, and nitrile rubber latex. In the present invention, the mass concentration of the rubber latex is preferably 40 to 69%, more preferably 40 to 50%. In the present invention, the mass ratio of the dry matrix of the refined slurry to the solid in the rubber latex is preferably 1:1.5 to 10.

[0062] In the present invention, the flocculant preferably comprises one or more of MgCl2, Mg(NO3)2, H2SO4, Mg(CH3COO)2, Al2(SO4)3 and KAl(SO4)2; the flocculant is preferably mixed in the form of a flocculant solution, and the mass concentration of the flocculant solution is preferably 15-20%. There is no special limitation on the mass of the flocculant in the present invention, as long as the flocculation is complete.

[0063] In the present invention, the temperature of the flocculation copolymerization is preferably 35-70 °C; the flocculation copolymerization is preferably carried out under stirring conditions. There is no special limitation on the time of the flocculation copolymerization in the present invention, as long as the flocculation is terminated.

[0064] In the present invention, after the flocculation copolymerization, it preferably further comprises successively kneading and vulcanizing the obtained material. There is no special limitation on the kneading and vulcanizing processes in the present invention, and those well-known to those skilled in the art can be used.

[0065] In the present invention, before kneading and after the flocculation copolymerization, it preferably further comprises successively dehydrating, washing, drying and dispersing the obtained material. There is no special limitation on the dehydration, washing, drying and dispersing processes in the present invention, and those well-known to those skilled in the art can be used.

[0066] Figure 1 It is a schematic flow chart of the preparation method provided by the present invention.

[0067] Figure 2 It is a particle size distribution diagram of the original sample of the coal gasification black water flocculant liquid. From Figure 2 it can be seen that the particle size of the coal gasification black water flocculant liquid is relatively large and the particle size distribution is relatively wide.

[0068] In the present invention, the particle size distribution is tested by ultrasonic wave using a laser particle size analyzer. Ethanol is used as the solution, and the mass ratio of the material to ethanol is 1:5. The test is carried out when the refractive index reaches 10-12.

[0069] In the present invention, for the cross-sectional morphology diagram, the tensile cross-section sample of the rubber composite material is adhered to the conductive adhesive, and after spraying gold, it is observed on a field emission electron microscope with a resolution of 2.0 nm (1 kV, WD = 1.5 mm, normal mode); magnification: 1000-50000 times; electron gun: cold cathode field emission electron source to observe the morphology and surface element distribution state of the particles.

[0070] In the present invention, the test conditions for the transmission electron microscope image are a maximum magnification of 1.1 million times, an acceleration voltage of 300 kV; a point resolution of 0.20 nm, a limit (information) resolution of 0.19 nm, and a minimum beam spot size of 0.2 nm; the energy resolution of the X-ray energy spectrometer is 130 eV.

[0071] Unless otherwise specified, the materials and equipment used in the present invention are all commercially available products in the art.

[0072] Next, the technical solutions in the present invention will be clearly and completely described in conjunction with the embodiments in the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments in the present invention without creative efforts shall fall within the protection scope of the present invention.

[0073] Example 1

[0074] Select 200 kg of gasification black water flocculant liquid from a coal chemical enterprise in Ordos City, and the mass concentration of the flocculant liquid is 7%;

[0075] Subject the gasification black water flocculant liquid to homogenization dispersion and sedimentation concentration in sequence to obtain a gasification black water concentrated liquid with a mass concentration of 30%;

[0076] Add sodium polyacrylate as a dispersant to the gasification black water flocculant liquid. The addition amount of the dispersant is 0.5% (0.07 kg) of the dry matrix of the gasification black water flocculant liquid, and stir strongly for 20 min; pump the uniformly stirred liquid into a wet vertical stirring mill, stir and grind for 30 min. The particle size D90 of the solid particles in the ground liquid is 17.06 μm, and D50 is 5.04 μm; pump the ground liquid into a high-gradient magnetic separator for magnetic separation. The magnetic separation intensity is 1000 Gauss, and the magnetic separation time is 3 min to obtain a magnetically separated suspension;

[0077] Adjust the pH value of the magnetically separated suspension to 9, then stir and age at 35 °C for 0.5 h, and perform sieving treatment on the aged system to obtain 47 kg of refined slurry. The particle size of the solid particles in the refined slurry is D90 = 17.06 μm, and the mass concentration of the refined slurry is 30%;

[0078] Pump the refined slurry into a flocculation stirrer, and then add 70 kg of natural rubber latex (mass concentration of 40%); add a 20% Al2(SO4)3 flocculant solution through a peristaltic pump, and stir at 60 °C for flocculation copolymerization until flocculation terminates; filter and wash the obtained liquid three times with water, dry and then disperse to obtain rubber composite powder;

[0079] Subject the obtained rubber composite powder to mixing and vulcanization in sequence to obtain the rubber composite material;

[0080] Figure 3 It is the particle size distribution diagram of the gasification black water concentrated liquid after grinding and peeling.

[0081] Example 2

[0082] Select 200 kg of the gasification black water flocculant solution from a coal chemical enterprise in Ordos City, and the mass concentration of the flocculant solution is 8%;

[0083] Carry out homogenization dispersion and sedimentation concentration on the gasification black water flocculant solution in sequence to obtain a gasification black water concentrated solution with a mass concentration of 25%;

[0084] Add the dispersant sodium polyacrylate to the gasification black water flocculant solution. The addition amount of the dispersant is 0.65% (0.104 kg) of the dry matrix of the gasification black water flocculant solution, and stir strongly for 30 min; Pump the evenly stirred liquid material into a wet vertical stirring mill and stir and grind for 45 min. The particle size D90 of the solid particles in the ground liquid material is 13.18 μm and D50 is 3.82 μm; Pump the ground liquid material into a high-gradient magnetic separator for magnetic separation. The magnetic separation intensity is 1100 Gauss and the magnetic separation time is 2 min to obtain a magnetically separated suspension;

[0085] Adjust the pH value of the magnetically separated suspension to 9, then stir and age at 40 °C for 1 h, and carry out sieving treatment on the aged system to obtain 64 kg of refined slurry. The particle size of the solid particles in the refined slurry is D90 = 13.18 μm, and the mass concentration of the refined slurry is 25%;

[0086] Pump the refined slurry into a flocculation stirrer, and then add 72 kg of natural rubber latex (mass concentration of 45%); Add a 20% Al2(SO4)3 flocculant solution through a peristaltic pump and carry out flocculation copolymerization by stirring at 60 °C until flocculation terminates; Filter and wash the obtained liquid material three times, dry it and then break it up to obtain rubber composite powder;

[0087] Carry out mixing and vulcanization on the obtained rubber composite powder in sequence to obtain the rubber composite material;

[0088] Figure 4 It is the particle size distribution diagram of the gasification black water concentrated solution after grinding and peeling.

[0089] Example 3

[0090] Select 200 kg of the gasification black water flocculant solution from a coal chemical enterprise in Ordos City, and the mass concentration of the flocculant solution is 10%;

[0091] Carry out homogenization dispersion and sedimentation concentration on the gasification black water flocculant solution in sequence to obtain a gasification black water concentrated solution with a mass concentration of 20%;

[0092] Add sodium polyacrylate as a dispersant to the coal gasification black water flocculant. The addition amount of the dispersant is 0.65% (0.13 kg) of the dry matrix of the coal gasification black water flocculant, and stir strongly for 30 min; pump the evenly stirred liquid into a wet vertical stirring mill, and stir and abrade for 60 min. The particle size D90 of the solid particles in the abraded liquid is 11.2 μm, and D50 is 3.71 μm; pump the abraded liquid into a high-gradient magnetic separator for magnetic separation. The magnetic separation intensity is 1200 gauss, and the magnetic separation time is 1.5 min to obtain the magnetically separated suspension.

[0093] Adjust the pH value of the magnetically separated suspension to 9.5, then stir and age at 45 °C for 1.5 h, and screen the aged system to obtain 100 kg of refined slurry. The particle size of the solid particles in the refined slurry is D90 = 11.2 μm, and the mass concentration of the refined slurry is 20%.

[0094] Pump the refined slurry into a flocculation stirrer, and then add 80 kg of natural rubber latex (mass concentration of 50%); add a 20% Al2(SO4)3 flocculant solution through a peristaltic pump, and stir at 60 °C for flocculation copolymerization until flocculation terminates; filter and wash the obtained liquid three times with water, dry it, and then break it up to obtain rubber composite powder.

[0095] Carry out mixing and vulcanization on the obtained rubber composite powder in sequence to obtain the rubber composite material.

[0096] Figure 5 It is the particle size distribution diagram of the coal gasification black water concentrate particles after abrasion.

[0097] Example 4

[0098] Select 200 kg of coal gasification black water flocculant from a coal chemical enterprise in Ordos City. The mass concentration of the flocculant is 10%.

[0099] Carry out homogenization dispersion and sedimentation concentration on the coal gasification black water flocculant in sequence to obtain a coal gasification black water concentrate with a mass concentration of 25%.

[0100] Add sodium polyacrylate as a dispersant to the coal gasification black water flocculant. The addition amount of the dispersant is 0.7% (0.14 kg) of the dry matrix of the coal gasification black water flocculant, and stir strongly for 30 min; pump the evenly stirred liquid into a wet vertical stirring mill, and stir and abrade for 90 min. The particle size D90 of the solid particles in the abraded liquid is 10.98 μm, and D50 is 3.64 μm; pump the abraded liquid into a high-gradient magnetic separator for magnetic separation. The magnetic separation intensity is 1000 gauss, and the magnetic separation time is 3 min to obtain the magnetically separated suspension.

[0101] Adjust the pH value of the suspension after magnetic separation to 10, then stir and age it at 50 °C for 1.5 h. Screen the aged system to obtain 80 kg of refined slurry. The particle size of the solid particles in the refined slurry is D90 = 10.98 μm, and the mass concentration of the refined slurry is 25%;

[0102] Pump the refined slurry into a flocculation stirrer, and then add 100 kg of natural rubber latex (mass concentration 40%); Add a 20% Al2(SO4)3 flocculant solution through a peristaltic pump, and stir at 60 °C for flocculation copolymerization until flocculation terminates; Filter, wash the obtained liquid three times with water, dry and then break it up to obtain rubber composite powder;

[0103] Carry out mixing and vulcanization on the obtained rubber composite powder in sequence to obtain the rubber composite material;

[0104] Figure 6 It is the particle size distribution diagram of the coal gasification black water concentrate after abrasion.

[0105] Example 5

[0106] Select 200 kg of coal gasification black water flocculant from a coal chemical enterprise in Ordos City. The mass concentration of the flocculant is 8%;

[0107] Carry out homogenization dispersion and sedimentation concentration on the coal gasification black water flocculant in sequence to obtain a coal gasification black water concentrate with a mass concentration of 30%;

[0108] Add the dispersant sodium polyacrylate to the coal gasification black water flocculant. The addition amount of the dispersant is 0.8% (0.128 kg) of the dry matrix of the coal gasification black water flocculant, and stir strongly for 30 min; Pump the uniformly stirred liquid into a wet vertical stirrer mill and stir and abrade for 90 min. The particle size of the solid particles in the abraded liquid is D90 = 7.37 μm and D50 = 2.74 μm; Pump the abraded liquid into a high-gradient magnetic separator for magnetic separation. The magnetic separation intensity is 1100 Gauss and the magnetic separation time is 1 min to obtain the suspension after magnetic separation;

[0109] Adjust the pH value of the suspension after magnetic separation to 10, then stir and age it at 60 °C for 1 h. Screen the aged system to obtain 54 kg of refined slurry. The particle size of the solid particles in the refined slurry is D90 = 7.37 μm, and the mass concentration of the refined slurry is 30%;

[0110] The refined slurry is pumped into a flocculation stirrer, and then 71 kg of natural rubber latex (with a mass concentration of 45%) is added; a 20% Al2(SO4)3 flocculant solution is added through a peristaltic pump, and flocculation copolymerization is carried out by stirring at 60 °C until flocculation terminates; the obtained liquid material is filtered, washed with water three times, dried and then broken up to obtain rubber composite powder;

[0111] The obtained rubber composite powder is successively kneaded and vulcanized to obtain the rubber composite material;

[0112] Figure 7 It is the particle size distribution diagram of the coal gasification black water concentrate after abrasion.

[0113] Example 6

[0114] 200 kg of coal gasification black water flocculant liquid from a certain coal chemical enterprise in Ordos City is selected, and the mass concentration of the flocculant liquid is 7%;

[0115] The coal gasification black water flocculant liquid is successively homogenized, dispersed and settled and concentrated to obtain a coal gasification black water concentrate with a mass concentration of 20%;

[0116] Sodium polyacrylate as a dispersant is added to the coal gasification black water flocculant liquid, and the addition amount of the dispersant is 1% (0.14 kg) of the dry matrix of the coal gasification black water flocculant liquid, and it is strongly stirred for 30 min; the uniformly stirred liquid material is pumped into a wet vertical stirring mill, and stirred and abraded for 90 min. The particle size D90 of the solid particles in the abraded liquid material is 5.61 μm, and D50 is 2.06 μm; the abraded liquid material is pumped into a high-gradient magnetic separator for magnetic separation, the magnetic separation intensity is 1200 Gauss, and the magnetic separation time is 2 min to obtain the magnetic-separated suspension;

[0117] The pH value of the magnetic-separated suspension is adjusted to 10, and then it is stirred and aged at 65 °C for 1.5 h. The aged system is sieved to obtain 70 kg of refined slurry. The particle size of the solid particles in the refined slurry is D90 of 5.61 μm, and the mass concentration of the refined slurry is 20%;

[0118] The refined slurry is pumped into a flocculation stirrer, and then 56 kg of natural rubber latex (with a mass concentration of 50%) is added; a 20% Al2(SO4)3 flocculant solution is added through a peristaltic pump, and flocculation copolymerization is carried out by stirring at 60 °C until flocculation terminates; the obtained liquid material is filtered, washed with water three times, dried and then broken up to obtain rubber composite powder;

[0119] The obtained rubber composite powder is successively kneaded and vulcanized to obtain the rubber composite material;

[0120] Figure 8 It is the particle size distribution diagram of the coal gasification black water concentrate after abrasion.

[0121] Figure 12 is a physical picture of the rubber composite powder Figure 13 is a physical picture of the rubber composite material obtained after vulcanization Figure 14 is a SEM picture of the rubber composite material obtained after vulcanization Figure 15 is a TEM picture of the rubber composite material obtained after vulcanization. It can be seen from Figures 12 - 15 that the distribution of fine coal gasification slag in the powdered rubber is relatively uniform, without obvious agglomeration, and has good compatibility with the rubber matrix

[0122] Comparative Example 1

[0123] Select 200 kg of coal gasification black water flocculant liquid from a certain coal chemical enterprise in Ordos City. The mass concentration of the flocculant liquid is 7.5%;

[0124] Perform homogenization dispersion and sedimentation concentration on the coal gasification black water flocculant liquid in sequence to obtain a coal gasification black water concentrated liquid with a mass concentration of 40%;

[0125] Add the dispersant sodium polyacrylate to the coal gasification black water flocculant liquid. The addition amount of the dispersant is 2% (0.3 kg) of the dry matrix of the coal gasification black water flocculant liquid, and stir strongly for 40 min; Pump the uniformly stirred liquid into a wet vertical stirring mill, stir and abrade for 3 min. The particle size D90 of the solid particles in the abraded liquid is 82.2 μm; Pump the abraded liquid into a high-gradient magnetic separator for magnetic separation. The magnetic separation intensity is 850 Gauss, and the magnetic separation time is 3 min to obtain a magnetically separated suspension;

[0126] Adjust the pH value of the magnetically separated suspension to 11, then stir and age at 35 °C for 0.5 h, pour out the supernatant of the aged system to obtain 37.5 kg of refined slurry. The particle size of the solid particles in the refined slurry is D90 of 82.2 μm, and the mass concentration of the refined slurry is 40%;

[0127] Pump the refined slurry into a flocculation stirrer, and then add 67 kg of natural rubber latex (mass concentration of 45%); Add a 25% Al2(SO4)3 flocculant solution through a peristaltic pump, and stir for flocculation copolymerization at 60 °C until flocculation terminates; Filter and wash the obtained liquid three times with water, dry and then disperse to obtain rubber composite powder;

[0128] Carry out mixing and vulcanization on the obtained rubber composite powder in sequence to obtain the rubber composite material;

[0129] Figure 9 is the particle size distribution diagram of the coal gasification black water concentrated liquid after abrasion

[0130] Figure 16SEM image of the obtained rubber composite powder. Starting from Figure 16 It can be seen from the cross-sectional morphology of the coal gasification slag rubber composite material at this time that due to the large particle size, the surface binding ability is small, and the binding ability with rubber is poor.

[0131] Comparative Example 2

[0132] Select 200 kg of coal gasification black water flocculant liquid from a certain coal chemical enterprise in Ordos City, and the mass concentration of the flocculant liquid is 7%;

[0133] The coal gasification black water flocculant liquid is homogenized, dispersed, settled and concentrated in sequence to obtain a coal gasification black water concentrate with a mass concentration of 20%;

[0134] Add the dispersant sodium polyacrylate to the coal gasification black water flocculant liquid, and the addition amount of the dispersant is 0.5% (0.07 kg) of the dry matrix of the coal gasification black water flocculant liquid, and stir strongly for 20 min; pump the uniformly stirred liquid to a wet vertical stirrer mill, stir and abrade for 5 min, and the particle size D90 of the solid particles in the abraded liquid is 79.06 μm; pump the abraded liquid to a high-gradient magnetic separator for magnetic separation, the magnetic separation intensity is 900 Gauss, and the magnetic separation time is 3 min to obtain the magnetically separated suspension;

[0135] Adjust the pH value of the magnetically separated suspension to 8, then stir and age at 40 °C for 1.5 h, and screen the aged system to obtain 70 kg of refined slurry. The particle size of the solid particles in the refined slurry is D90 of 79.06 μm, and the mass concentration of the refined slurry is 20%;

[0136] Pump the refined slurry to a flocculation stirrer, and then add 56 kg of natural rubber latex (mass concentration of 50%); add 20% Al2(SO4)3 flocculant solution through a peristaltic pump, and stir and carry out flocculation copolymerization at 60 °C until flocculation terminates; filter and wash the obtained liquid three times with water, dry and then disperse to obtain rubber composite powder;

[0137] The obtained rubber composite powder is kneaded and vulcanized in sequence to obtain the rubber composite material;

[0138] Figure 10 It is the particle size distribution diagram of the coal gasification black water concentrate particles after abrasion.

[0139] Comparative Example 3

[0140] Select 200 kg of coal gasification black water flocculant liquid from a certain coal chemical enterprise in Ordos City, and the mass concentration of the flocculant liquid is 8%;

[0141] The coal gasification black water flocculant liquid is homogenized, dispersed, settled and concentrated in sequence to obtain a coal gasification black water concentrate with a mass concentration of 50%;

[0142] Dispersant sodium polyacrylate was added to the coal gasification black water flocculant solution, and the addition amount of the dispersant was 0.5% (0.08 kg) of the dry matrix of the coal gasification black water flocculant solution, and it was vigorously stirred for 20 min; the uniformly stirred feed liquid was pumped into a wet vertical stirring mill and stirred and abraded for 120 min. The particle size D90 of the solid particles in the abraded feed liquid was 61.95 μm; the abraded feed liquid was pumped into a high-gradient magnetic separator for magnetic separation. The magnetic separation intensity was 1500 Gauss, and the magnetic separation time was 3 min to obtain the suspended liquid after magnetic separation;

[0143] The pH value of the suspended liquid after magnetic separation was adjusted to 10, and then it was stirred and aged at 50 °C for 1.5 h. The aged system was sieved to obtain 32 kg of refined slurry. The particle size of the solid particles in the refined slurry was D90 of 61.95 μm, and the mass concentration of the refined slurry was 50%;

[0144] The refined slurry was pumped into a flocculation stirrer, and then 64 kg of natural rubber latex (mass concentration of 50%) was added; 20% Al2(SO4)3 flocculant solution was added through a peristaltic pump, and flocculation copolymerization was carried out by stirring at 60 °C until flocculation terminated; the obtained feed liquid was filtered, washed with water three times, dried and then dispersed to obtain rubber composite powder;

[0145] The obtained rubber composite powder was successively mixed and vulcanized to obtain the rubber composite material;

[0146] Figure 11 It is the particle size distribution diagram of the coal gasification black water concentrate particles after abrasion.

[0147] Performance Test

[0148] The mechanical properties of the rubber composite materials obtained in Examples 1 to 6 and Comparative Examples 1 to 3 were tested. Among them, the tensile strength was tested according to the GB / T531-99 test standard, the tear strength was tested according to the GB / T529-99 test standard, the modulus was tested according to the GB / T531-99 test standard, and the elongation at break was tested according to the GB / T531-99 test standard;

[0149] The obtained test results are shown in Table 1;

[0150] Table 1 Mechanical properties of the rubber composite materials obtained in Examples 1 to 6 and Comparative Examples 1 to 3

[0151]

[0152] It can be seen from Table 1 that the mechanical properties from Example 1 to Example 6 are correlated with the particle size in the examples, and the smaller the particle size, the better the mechanical properties.

[0153] Although the above embodiments have described the present invention in detail, they are only a part of the embodiments of the present invention, rather than all embodiments. Other embodiments can be obtained based on these embodiments without creative efforts, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A method for preparing a rubber composite material, characterized in that: The following steps are involved: The concentrated liquid obtained by concentrating the coal gasification black water flocculant is mixed with a dispersant, and then subjected to grinding and magnetic separation in sequence to obtain a suspension after magnetic separation; the mass concentration of the concentrated liquid is 15-45%; The suspension after magnetic separation is adjusted to be alkaline, and then aged and sieved in sequence to obtain a refined slurry; the particle size D90 of the solid particles in the refined slurry is 2-18 μm; The refined slurry, rubber latex and flocculant are mixed and flocculated to obtain the rubber composite material.

2. The preparation method according to claim 1, characterized in that: The dispersant includes one or more of sodium polyacrylate, sodium stearate, sodium hexametaphosphate, sodium tripolyphosphate and sodium citrate; The mass of the dispersant is 0.3-5.5% of the mass of the dry matrix of the concentrate.

3. The preparation method according to claim 1, characterized in that: The grinding time is 10 to 120 minutes.

4. The preparation method according to claim 1, characterized in that: The intensity of the magnetic separation is 800-1600 Gauss, and the time of the magnetic separation is 1-3 minutes.

5. The preparation method according to claim 1, characterized in that: The alkaline pH value is 8.5 to 11.0; The aging temperature is 35-65° C.; the aging is carried out under stirring, and the stirring time is 0.5-1.5 h.

6. The preparation method according to claim 1, characterized in that: The rubber latex comprises one or more of styrene-butadiene rubber latex, natural rubber latex and nitrile-butadiene rubber latex; The mass concentration of the rubber latex is 40-69%; The mass ratio of the dry matrix of the refined slurry to the solid in the rubber latex is 1:1.5-10.

7. The preparation method according to claim 1, characterized in that: The flocculant includes one or more of MgCl2, Mg(NO3)2, H2SO4, Mg(CH3COO)2, Al2(SO4)3 and KAl(SO4)2; The flocculant is mixed in the form of a flocculant solution, and the mass concentration of the flocculant solution is 15-20%.

8. The preparation method according to claim 1, characterized in that: The flocculation copolymerization temperature is 35-70° C., and the flocculation copolymerization is carried out under stirring conditions.

9. The preparation method according to claim 1, characterized in that: After the flocculation copolymerization, the obtained materials are mixed and vulcanized in sequence.

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