CN112980523B - Coal water slurry and additive mixed with methanol to olefin wastewater - Google Patents
Coal water slurry and additive mixed with methanol to olefin wastewater Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/106—Liquid carbonaceous fuels containing additives mixtures of inorganic compounds with organic macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
- C10L1/326—Coal-water suspensions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/12—Inorganic compounds
- C10L1/1233—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
- C10L1/125—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof water
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/1802—Organic compounds containing oxygen natural products, e.g. waxes, extracts, fatty oils
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
- C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2462—Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
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Abstract
The invention discloses a water-coal-slurry and an additive for preparing olefin wastewater by blending methanol, wherein the additive is prepared from sodium sulfomethyl humate, laurinol polyoxyethylene ether, sodium polyepoxysuccinate, xanthan gum and water, wherein the sodium sulfomethyl humate, the laurinol polyoxyethylene ether, the sodium polyepoxysuccinate and the xanthan gum account for 30-50% of the total mass of the additive; the water-coal slurry is prepared from the methanol-to-olefin wastewater, the additive, raw coal and pulping water according to the mass ratio of the methanol-to-olefin wastewater to the pulping water of 0.5-3:7-9.5 and the additive amount of 0.15-0.4% of the mass of dry base coal. The additive is used for preparing the water-coal-slurry by blending DMTO wastewater, has the advantages of small usage amount, good dispersion performance and high stability, and the slurry forming performance is not changed due to the existence of oily substances, metal ions and toxic substances in the DMTO wastewater, so that the preparation of qualified water-coal-slurry by the DMTO wastewater is realized, and the additive has positive guiding effect on water saving and resource utilization of a coal chemical system.
Description
Technical Field
The invention belongs to the technical field of coal water slurry, and particularly relates to a coal water slurry and an additive for blending methanol-to-olefin (DMTO) wastewater.
Background
The water-coal slurry is a mixture prepared from 58-65% of coal with different particle size distribution, 35-42% of water and less than 1% of chemical additives, is a coal-based liquid fuel, has the characteristics of good fluidity and stability, easy storage, atomization combustion, high combustion efficiency and low pollution, can be used as a kiln fuel or a synthetic gas raw material, is a cheaper clean fuel, and can replace heavy oil to relieve the energy safety problem of petroleum shortage.
DMTO is a technology for preparing ethylene and propylene from methanol by taking coal or natural gas as a raw material. The waste water generated in the DMTO process has high COD, contains a small amount of petroleum substances and toxic substances such as ketone, alcohol, aromatic hydrocarbon and the like which are difficult to biodegrade, and the water quality is greatly influenced by a production device and fluctuates. The matched wastewater treatment process of the DMTO device which is put into operation at home at present mainly comprises the following steps: oil removal pretreatment, biochemical treatment, advanced treatment and reclaimed water recycling treatment. The oil removal pretreatment and the reclaimed water recycling treatment technology are mature, oil removal-air floatation oil removal and double-membrane desalination processes are adopted, the difficulty of biochemical treatment and advanced treatment processes is high, the traditional process and various improved processes are all used, the treatment cost is high, the effects are uneven, and the applicable biochemical treatment and advanced treatment processes are also in exploration.
In recent years, more and more coal chemical industry in China is greatly developing a DMTO technology, if DMTO wastewater treatment in a coal chemical industry system is combined with a coal water slurry preparation technology, the technology for preparing the coal water slurry by using the DMTO wastewater is researched and developed, the treatment path of the DMTO wastewater is widened, the difficult problem of treating the DMTO wastewater is relieved to a certain extent, and the treatment cost is reduced, so that the industrial water conservation and the recycling are realized. The development of the water-coal-slurry additive suitable for DMTO wastewater pulping also becomes a new research direction of additive preparation technology.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an additive which has small dosage and excellent slurry forming performance and can be used for preparing coal water slurry from DMTO wastewater and the coal water slurry mixed with methanol to prepare olefin wastewater.
The additive for solving the technical problems is prepared from sodium sulfomethyl humate, laureth, polyepoxysuccinate sodium, xanthan gum and water, wherein the sodium sulfomethyl humate, laureth, polyepoxysuccinate sodium and xanthan gum account for 30-50% of the total mass of the additive, and the mass ratio of the sodium sulfomethyl humate, the laureth, the polyepoxysuccinate sodium and the xanthan gum is 1-7:0.1-0.5:0.05-0.2:0.01-0.04.
The additive is used for preparing the coal water slurry by doping DMTO wastewater, and preferably comprises sodium sulfomethyl humate, laurinol polyoxyethylene ether, polyepoxysuccinate and xanthan gum in a mass ratio of 3-5:0.15-0.3:0.08-0.15:0.015-0.025, and optimally 4:0.2:0.1:0.02.
The preparation method of the additive for preparing the coal water slurry by blending DMTO wastewater comprises the following steps: according to the mass ratio of the raw materials, adding sodium sulfomethyl humate, laureth and polyepoxysuccinate into water, stirring for 10-20 minutes at the rotating speed of 40-60 r/min, then adding xanthan gum, stirring for 30-40 minutes at the rotating speed of 60-80 r/min, discharging after uniform stirring, and analyzing and checking to obtain the additive.
The water-coal-slurry mixed with DMTO wastewater is prepared by the following method: according to the mass ratio of the DMTO wastewater to the pulping water of 0.5-3:7-9.5, the dosage of the additive is 0.15-0.4% of the mass of dry base coal, the DMTO wastewater and the additive are firstly mixed uniformly in a container with stirring, the obtained mixed liquid, crushed raw coal and pulping water are sent into a coal mill together for grinding, and the water-coal-slurry prepared by blending the DMTO wastewater is obtained after discharging.
In the water-coal slurry doped with the DMTO wastewater, the mass ratio of the DMTO wastewater to the pulping water is preferably 1.5-2.5:7.5-8.5, and the dosage of the additive is 0.25-0.35% of the mass of dry coal.
The beneficial effects of the invention are as follows:
the additive is used for preparing the coal water slurry by blending DMTO wastewater, and has the advantages of small usage amount, good dispersion performance and high stability. Sodium sulfomethyl humate in the additive formula has excellent dispersion performance, laureth and xanthan gum have better emulsification effect on oily substances in DMTO wastewater, the laureth can uniformly disperse and suspend the oily substances in a coal water slurry system, and the xanthan gum has good stabilization effect on the coal water slurry system. The polyepoxysuccinate sodium has good dispersion stabilization effect on metal ions such as calcium, magnesium and other toxic substances in wastewater. The pulping performance of the additive is not changed due to the existence of oily substances, metal ions and toxic substances in DMTO wastewater, so that the preparation of qualified coal water slurry from the DMTO wastewater is realized, the problems of high treatment difficulty and high cost of the DMTO wastewater are solved, and the additive has a positive guiding effect on water conservation and resource utilization of a coal chemical system.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to these examples.
Example 1
252.10g of sodium sulfomethyl humate, 25.21g of laureth, 20.17g of polyepoxysuccinate and 700g of water are added into a stirring tank at normal temperature and normal pressure, stirring is carried out for 10 minutes at a rotating speed of 60 revolutions per minute, then 2.52g of xanthan gum is added, stirring is continued for 40 minutes, the rotating speed is 80 revolutions per minute, the mass ratio of sodium sulfomethyl humate, laureth, polyepoxysuccinate to xanthan gum is 1:0.1:0.08:0.01, and the additive for preparing the coal water slurry by doping DMTO wastewater is obtained after the product is completely dissolved and uniformly stirred.
Example 2
277.78g of sodium sulfomethyl humate, 13.89g of laureth, 6.94g of polyepoxysuccinate and 700g of water are added into a stirring tank at normal temperature and normal pressure, stirring is carried out for 15 minutes at a rotating speed of 50 revolutions per minute, then 1.39g of xanthan gum is added, stirring is continued for 35 minutes, the rotating speed is 70 revolutions per minute, the mass ratio of sodium sulfomethyl humate, laureth, polyepoxysuccinate to xanthan gum is 4:0.2:0.1:0.02, and the additive for preparing the coal water slurry by doping DMTO wastewater is obtained after the product is completely dissolved and uniformly stirred.
Example 3
273.55g of sodium sulfomethyl humate, 18.24g of laureth, 6.84g of polyepoxysuccinate and 700g of water are added into a stirring tank at normal temperature and normal pressure, stirring is carried out for 20 minutes at a rotating speed of 40 revolutions per minute, then 1.37g of xanthan gum is added, stirring is continued for 30 minutes, the rotating speed is 75 revolutions per minute, the mass ratio of sodium sulfomethyl humate, laureth, polyepoxysuccinate to xanthan gum is 6:0.4:0.15:0.03, and the additive for preparing the coal water slurry by doping DMTO wastewater is obtained after the product is completely dissolved and uniformly stirred.
Example 4
According to the proportion of DMTO wastewater to pulping water of 2:8, the dosage of the additive is 0.3% of the mass of dry base coal, the DMTO wastewater and the additive prepared in the embodiment 2 are firstly mixed uniformly in a container with stirring, the obtained mixed liquid, crushed raw coal and pulping water are sent into a coal mill together for grinding, and the water-coal-slurry prepared by blending the DMTO wastewater is obtained after discharging.
The additives of example 2 were replaced with the additives of comparative examples 1 to 9 shown in Table 1, respectively, and coal slurries were prepared in the same amount as in Table 2 according to the method of example 4, and the concentrations, viscosities and stabilities of the obtained coal slurries were measured by the following specific test methods:
(1) And (3) measuring the concentration of the coal water slurry: 2-3 g of the water-coal-slurry is weighed and placed in a rapid moisture tester, the testing temperature is 105 ℃, the testing time is 30 minutes, and the final reading displayed by the tester is the water-coal-slurry concentration.
(2) And (3) measuring the viscosity of the coal water slurry: reference is made to the GB/T18856.4 test method.
(3) Evaluation of stability of coal water slurry: after the water-coal-slurry is placed in a closed container for a certain time, the surface of the slurry has obvious water separation, and the original slurry flow pattern cannot be recovered by stirring with a glass rod, so that the slurry is hard precipitate; soft precipitation occurs if there is no bleeding on the surface of the slurry, or if there is bleeding but the original slurry state can be restored by stirring. The volume of the water separation part is weighed, and the ratio of the water separation amount to the volume of the coal water slurry is called the water separation rate. The test results are shown in Table 2.
Table 1 compares the product formulation compositions
| Contrast product | Component (A) | Mass ratio |
| Comparative example 1 | Laurinol polyoxyethylene ether and sodium lignin sulfonate | 1:9 |
| Comparative example 2 | Laurinol polyoxyethylene ether and sodium naphthalene sulfonate formaldehyde condensate | 1:9 |
| Comparative example 3 | Laurinol polyoxyethylene ether and sodium humate | 1:9 |
| Comparative example 4 | Laurinol polyoxyethylene ether and sodium polyacrylate | 1:9 |
| Comparative example 5 | Sodium laurinol polyoxyethylene ether and polystyrene sulfonate | 1:9 |
| Comparative example 6 | Sodium humate+sodium lignin sulfonate | 9:1 |
| Comparative example 7 | Sodium humate+sodium naphthalene sulfonate formaldehyde condensate | 9:1 |
| Comparative example 8 | Sodium humate+sodium polyacrylate | 9:1 |
| Comparative example 9 | Sodium humate + sodium polystyrene sulfonate | 9:1 |
Table 2 experimental results
As shown in Table 2, when the dosage of the additive is 0.3% of the mass of the dry base coal, the prepared water-coal-slurry has excellent slurry forming performance, and all indexes can meet the requirements of water-coal-slurry technical indexes. The comparative example product can only prepare the coal water slurry with the concentration of 57.3 to 60.2 percent when the dosage of the coal water slurry additive is 0.5 to 0.8 percent, namely the comparative example product is used for preparing the coal water slurry with the dosage being large, and the prepared coal water slurry has lower concentration, higher viscosity and poorer stability than the coal water slurry prepared by the additive.
Claims (3)
1. The utility model provides a mix coal water slurry of methyl alcohol system olefin waste water which characterized in that: according to the mass ratio of the methanol-to-olefin wastewater to the pulping water of 0.5-3:7-9.5, the dosage of the additive is 0.15-0.4% of the mass of the dry base coal, the methanol-to-olefin wastewater and the additive are firstly mixed uniformly in a container with stirring, the obtained mixed solution, crushed raw coal and pulping water are sent into a coal mill together for grinding, and the water-coal slurry mixed with the methanol-to-olefin wastewater is obtained after discharging;
the additive is prepared from sodium sulfomethyl humate, laurinol polyoxyethylene ether, sodium polyepoxysuccinate, xanthan gum and water, wherein the sodium sulfomethyl humate, the laurinol polyoxyethylene ether, the sodium polyepoxysuccinate and the xanthan gum account for 30-50% of the total mass of the additive, and the mass ratio of the sodium sulfomethyl humate to the laurinol polyoxyethylene ether to the sodium polyepoxysuccinate to the xanthan gum is 3-5:0.15-0.3:0.08-0.15:0.015-0.025.
2. The slurry of coal water blended with methanol-to-olefins wastewater of claim 1, wherein: the mass ratio of the sodium sulfomethyl humate to the laurinol polyoxyethylene ether to the sodium polyepoxysuccinate to the xanthan gum is 4:0.2:0.1:0.02.
3. The slurry of coal water blended with methanol-to-olefins wastewater of claim 1, wherein: the mass ratio of the methanol-to-olefin wastewater to the pulping water is 1.5-2.5:7.5-8.5, and the dosage of the additive is 0.25-0.35% of the mass of the dry coal.
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| CN102796576A (en) * | 2012-09-12 | 2012-11-28 | 安徽理工大学 | Method for preparing coal water slurry by utilizing acrylonitrile waste water |
| CN103708632B (en) * | 2014-01-13 | 2015-04-01 | 湖南东盈煤化工技术开发有限公司 | Grey water antiscale dispersion agent for gasification |
| CN110482716A (en) * | 2019-08-31 | 2019-11-22 | 天津正达科技有限责任公司 | A kind of dedicated non-phosphorus scale dispersing agent of coal gasification buck and preparation method thereof, application |
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Non-Patent Citations (4)
| Title |
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| "聚环氧琥珀酸钠洗涤助剂的合成及性能";郭建维等;《广东工业大学学报》;20170331;第34卷(第2期);第17-22页 * |
| 周安宁等.水煤浆技术.《洁净煤技术》.中国矿业大学出版社,2010,第71-73页. * |
| 李建颖.黄原胶.《食品添加剂速查手册》.南开大学出版社,2017,第91页. * |
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