阅读说明：本技术 一种油泥-芦苇资源化利用方法及装置 (Oil sludge-reed resource utilization method and device ) 是由 程之勇 何静 张海艳 程彦森 谭立新 寇连星 于 2021-09-23 设计创作，主要内容包括：本发明涉及环保技术领域,公开了一种油泥-芦苇资源化利用方法及装置。该方法是将将油泥和芦苇按一定比例混合后压制成油泥-芦苇砖,在真空气化隧道窑内由室温逐渐加热到1900℃的温度,发生一系列还原、碳化反应,将得到的气体及生成的碳化物进行有效分离。该装置包括原料车间、油泥-芦苇砖窑车、进料真空室、真空气化隧道窑、出料真空室、卸料车间、低温区冷凝罐、中温区冷凝罐、高温区冷凝罐、储气罐及气体通道。本发明将芦苇和油泥完全资源化,把废料中的有用成分转化成附加值高的单一物质或简单混合物；余热得到充分利用；可广泛应用于赤泥、工业垃圾、生活垃圾、城市淤泥及各种矿渣等废料处理。(The invention relates to the technical field of environmental protection, and discloses a method and a device for resource utilization of oil sludge-reed. The method is that the oil sludge and the reed are mixed according to a certain proportion and then pressed into an oil sludge-reed brick, the oil sludge-reed brick is gradually heated to 1900 ℃ from room temperature in a vacuum gasification tunnel kiln to generate a series of reduction and carbonization reactions, and the obtained gas and the generated carbide are effectively separated. The device comprises a raw material workshop, an oil sludge-reed brick kiln car, a feeding vacuum chamber, a vacuum gasification tunnel kiln, a discharging vacuum chamber, a discharging workshop, a low-temperature region condensing tank, a medium-temperature region condensing tank, a high-temperature region condensing tank, an air storage tank and an air channel. The invention completely recycles the reed and the oil sludge, and converts useful components in the waste into single substances or simple mixtures with high added values; the waste heat is fully utilized; can be widely applied to the treatment of waste materials such as red mud, industrial garbage, household garbage, urban sludge, various slag and the like.)

1. A method for resource utilization of oil sludge-reed is characterized by comprising the following steps:

(1) drying the reed at the temperature of 100-150 ℃, and rolling and preparing reed powder with the particle size of less than 1 mm;

(2) evenly mixing oil sludge and reed powder in a weight ratio of 1 (0.5-1.5), and pressing the mixture into an oil sludge-reed brick;

(3) sending the oil sludge-reed bricks into a vacuum gasification tunnel kiln through an oil sludge-reed brick kiln car, heating the oil sludge-reed bricks to 1900 ℃ from room temperature by adopting electric energy, gasifying, decomposing and carbonizing water and organic matters in the oil sludge-reed bricks, and carrying out reduction and carbonization reactions with oxides, sulfides and nitrides in the oil sludge;

(4) the gas obtained in the step (3) is led out in sections from low to high according to the temperature, and single substances with high purity and high added value are respectively condensed or crystallized in the condensation tanks of corresponding temperature sections according to the liquefaction temperature points or the crystallization temperature points of different gas types;

(5) and (4) gradually cooling and discharging the carbide and the surplus carbon generated in the step (3) at the tail part of the vacuum gasification tunnel kiln, and further processing.

2. The method for recycling sludge-bulrush as claimed in claim 1, wherein the sludge-bulrush brick in the step (2) has a length of 240mm, a width of 120mm and a thickness of 60 mm.

3. The method for recycling sludge-bulrush as claimed in claim 1, wherein the chemical change of the components contained in the bulrush in the step (3) is as follows: protein, fat, nitrogen-free extract, C of cracking crude fiber into small molecules_nH_n、CO、H₂、N₂C, P₂O₅ 、K₂Gasifying O at high temperature, reacting CaO and charcoal to generate calcium carbide and CO, generating elemental S from sulfur in sulfide, and generating N from nitrogen in nitride₂(ii) a The chemical change of the components contained in the oil sludge is as follows: cracking organic matter into small molecule C_nH_n、CO、H₂、N₂Carbon, Al₂O₃Reacting with C under reducing atmosphere to generate Al₄C₃And CO gas, SiO₂Reacting with C to generate SiC and CO gas, reacting CaO with C to generate CaC₂And CO, MgO reacts with C to generate metal Mg, CO and Na₂O and K₂Gasifying O at high temperature, reacting ZnO with C to generate Zn, CO and Fe₂O₃React with C to generate Fe, CO and TiO₂React with C to produce TiC and CO gas, ZrO₂Reacting with C to generate ZrC and CO, generating S from sulfur in sulfide and N from nitrogen in nitride₂。

4. The method as claimed in claim 3, wherein the small molecule C generated by the cracking is used as the C resource_nH_nCondensing and separating in a low-temperature condensing tank to obtain high-temperature gasified P₂O₅ 、K₂O、Na₂O, S condensing and crystallizing in condensing tank at middle temperature region for separation, metal Mg vapor and metal Zn vaporCondensing and crystallizing in a condensing tank in a high-temperature area for separation, and separating CO and H in the gas₂、 N₂Sent to a gas storage tank through a gas channel for storage.

5. The method for recycling sludge-reed as claimed in claim 3, wherein the generated metal Fe is separated by a magnetic separator; mixing Al₄C₃、SiC、CaC₂TiC, ZrC and water, wherein Al₄C₃、CaC₂Reaction with water to form Al (OH)₃ 、Ca（OH）₂ And acetylene gas, and collecting and storing the obtained acetylene gas; the obtained Al (OH)₃ 、Ca（OH）₂Rinsing the mixture of SiC, TiC, ZrC and residual C with water, and separating into two groups of high value-added mixtures, wherein one group is Al (OH)₃ 、Ca（OH）₂And C, and the other group is a mixture of SiC, TiC and ZrC.

6. An oil sludge-reed resource utilization device, which is characterized in that the device is matched with the oil sludge-reed resource utilization method of any one of the claims 1 to 5, and comprises a raw material workshop, an oil sludge-reed brick kiln car, a feeding vacuum chamber, a vacuum gasification tunnel kiln, a discharging vacuum chamber, a discharging workshop, a low-temperature area condensing tank, a medium-temperature area condensing tank, a high-temperature area condensing tank, an air storage tank and an air channel; the raw material workshop, the feeding vacuum chamber, the vacuum gasification tunnel kiln, the discharging vacuum chamber and the discharging workshop are sequentially communicated and are conveyed through an oil sludge-reed brick kiln vehicle on a track; the vacuum gasification tunnel kiln comprises a preheating zone, a high-temperature zone and a cooling zone; the low-temperature area condensing tank, the medium-temperature area condensing tank and the high-temperature area condensing tank are arranged in a matched manner and distributed on the outer side of the vacuum gasification tunnel kiln; the gas storage tank is respectively connected with the low-temperature-area condensing tank, the medium-temperature-area condensing tank and the high-temperature-area condensing tank through gas channels.

7. The oil sludge-reed resource utilization device as claimed in claim 6, wherein two sets of the low-temperature-region condensing tank, the medium-temperature-region condensing tank and the high-temperature-region condensing tank are arranged and respectively placed on the left side and the right side of the vacuum gasification tunnel kiln.

8. The oil sludge-reed resource utilization device as claimed in claim 6, wherein the preheating zone and the cooling zone of the vacuum gasification tunnel kiln have the same structure, and the kiln wall of the vacuum gasification tunnel kiln sequentially comprises a metal shell, a low-temperature felt, a high-temperature insulating brick, a common ceramic pipe, a carbon fiber composite heat insulation board, a carbon fiber composite heat insulation graphite pipe, a carbon fiber composite heat insulation graphite plate and a graphite lining from outside to inside; the kiln wall of the high-temperature zone is sequentially provided with a metal shell, a low-temperature felt, a high-temperature insulating brick, a common ceramic pipe, a carbon fiber composite heat insulation plate, a carbon fiber composite heat insulation graphite pipe, a graphite lining and a graphite heating body from outside to inside.

9. The sludge-reed resource utilization device as claimed in claim 6, wherein the vacuum gasification tunnel kiln is introduced into the clean mixed gas stored in the gas storage tank through a pipeline for heat energy transfer.

Technical Field

The invention relates to the technical field of environmental protection, in particular to a method and a device for resource utilization of oil sludge-reed.

Background

The oil sludge sand is also called as oil-containing sludge and is an associated product in each link in the oil exploitation and enterprise refining processes; the oil sludge sand is a mixture of oil and water, generally exists in a physical form of water-in-oil and oil-in-water, and is an extremely stable emulsion suspension system. The oil sludge sand contains high-concentration toxic substances of petroleum hydrocarbon, a large amount of various metal elements such as potassium, sodium, iron, calcium, silicon, zinc and the like, and a large amount of water treatment agents such as a coagulant, a scale inhibitor, a bactericide and the like which are added in the production process. Due to the complexity of the components of the oil sludge sand, the environment can be greatly polluted due to improper disposal, and the human health is greatly damaged. At present, the oil sludge sand recycling treatment technology mainly comprises an extraction method, a chemical conditioning-mechanical separation method, a thermochemical method and the like, and mainly recovers crude oil; in addition, an incineration method, a safe landfill method, a solidification method, a biodegradation technology and the like are adopted; due to the laggard treatment technology, the obtained product has low added value, so that the economic benefit of an enterprise is low, the normal operation of the enterprise cannot be maintained, and the accumulation of oil sludge and sand causes environmental pollution.

The reed is a perennial aquatic or hygrophyte tall grass, grows beside an irrigation ditch, a river levee and a marshland and the like, particularly grows large reed at the intertidal zone of east-west yellow river, has low utilization rate and causes certain influence on the environment.

The two wastes have not been treated well so far. From the publications searched at present, there is no patent for comprehensive treatment and efficient utilization of the above two wastes in combination.

Disclosure of Invention

Aiming at the technical problems, the invention provides a method and a device for recycling oil sludge-reed.

Firstly, the invention provides a resource utilization method of oil sludge-reed, which comprises the following steps:

(1) drying the reed at the temperature of 100-150 ℃, and rolling and preparing reed powder with the particle size of less than 1 mm;

(2) evenly mixing oil sludge and reed powder in a weight ratio of 1 (0.5-1.5), and pressing the mixture into an oil sludge-reed brick;

(3) sending the oil sludge-reed bricks into a vacuum gasification tunnel kiln through an oil sludge-reed brick kiln car, heating the oil sludge-reed bricks to 1900 ℃ from room temperature by adopting electric energy, gasifying, decomposing and carbonizing water and organic matters in the oil sludge-reed bricks, and carrying out reduction and carbonization reactions with oxides, sulfides and nitrides in the oil sludge;

(4) the gas obtained in the step (3) is led out in sections from low to high according to the temperature, and single substances with high purity and high added value are respectively condensed or crystallized in the condensation tanks of corresponding temperature sections according to the liquefaction temperature points or the crystallization temperature points of different gas types;

(5) and (4) gradually cooling and discharging the carbide and the surplus carbon generated in the step (3) at the tail part of the vacuum gasification tunnel kiln, and further processing.

The above technical solution can be further optimized as follows:

the length of the oil sludge-reed brick in the step (2) is 240mm, the width of the oil sludge-reed brick is 120mm, and the thickness of the oil sludge-reed brick is 60 mm.

The chemical change of the components contained in the reed in the step (3) is as follows: protein, fat, nitrogen-free extract, C of cracking crude fiber into small molecules_nH_n、CO、H₂、N₂C, P₂O₅ 、K₂Gasifying O at high temperature, reacting CaO and charcoal to generate calcium carbide and CO, generating elemental S from sulfur in sulfide, and generating N from nitrogen in nitride₂(ii) a The chemical change of the components contained in the oil sludge is as follows: cracking organic matter into small molecule C_nH_n、CO、H₂、N₂Carbon, Al₂O₃Reacting with C under reducing atmosphere to generate Al₄C₃And CO gas, SiO₂Reacting with C to generate SiC and CO gas, reacting CaO with C to generate CaC₂And CO, MgO reacts with C to generate metal Mg, CO and Na₂O and K₂Gasifying O at high temperature, reacting ZnO with C to generate Zn, CO and Fe₂O₃React with C to generate Fe, CO and TiO₂React with C to produce TiC and CO gas, ZrO₂Reacting with C to generate ZrC and CO, generating S from sulfur in sulfide and N from nitrogen in nitride₂。

Small molecule C generated by the cracking_nH_nCondensing and separating in a low-temperature condensing tank to obtain high-temperature gasified P₂O₅ 、K₂O、Na₂O, S separating by condensing and crystallizing in condensing tank at middle temperature region, separating Mg vapor and Zn vapor by condensing and crystallizing in condensing tank at high temperature region, and separating CO and H₂、 N₂Sent to a gas storage tank through a gas channel for storage.

Separating the generated metal Fe by using a magnetic separator; mixing Al₄C₃、SiC、CaC₂TiC, ZrC and water, wherein Al₄C₃、CaC₂Reaction with water to form Al (OH)₃ 、Ca（OH）₂ And acetylene gas, and collecting and storing the obtained acetylene gas; the obtained Al (OH)₃ 、Ca（OH）₂Rinsing the mixture of SiC, TiC, ZrC and residual C with water, and separating into two groups of high value-added mixtures, wherein one group is Al (OH)₃ 、Ca（OH）₂And C, and the other group is a mixture of SiC, TiC and ZrC.

Secondly, the invention provides an oil sludge-reed resource utilization device which is matched with the oil sludge-reed resource utilization method and comprises a raw material workshop, an oil sludge-reed brick kiln car, a feeding vacuum chamber, a vacuum gasification tunnel kiln, a discharging vacuum chamber, a discharging workshop, a low-temperature region condensing tank, a medium-temperature region condensing tank, a high-temperature region condensing tank, an air storage tank and an air channel; the raw material workshop, the feeding vacuum chamber, the vacuum gasification tunnel kiln, the discharging vacuum chamber and the discharging workshop are sequentially communicated and are conveyed through an oil sludge-reed brick kiln vehicle on a track; the vacuum gasification tunnel kiln comprises a preheating zone, a high-temperature zone and a cooling zone; the low-temperature area condensing tank, the medium-temperature area condensing tank and the high-temperature area condensing tank are arranged in a matched manner and distributed on the outer side of the vacuum gasification tunnel kiln; the gas storage tank is respectively connected with the low-temperature-area condensing tank, the medium-temperature-area condensing tank and the high-temperature-area condensing tank through gas channels.

The above technical solution can be further optimized as follows:

and the low-temperature area condensing tank, the medium-temperature area condensing tank and the high-temperature area condensing tank are respectively arranged at the left side and the right side of the vacuum gasification tunnel kiln.

The structure of the preheating zone and the cooling zone of the vacuum gasification tunnel kiln is the same, and the kiln wall of the vacuum gasification tunnel kiln sequentially comprises a metal shell, a low-temperature felt, a high-temperature insulating brick, a common ceramic pipe, a carbon fiber composite heat insulation plate, a carbon fiber composite heat insulation graphite pipe, a carbon fiber composite heat insulation graphite plate and a graphite lining from outside to inside; the kiln wall of the high-temperature zone is sequentially provided with a metal shell, a low-temperature felt, a high-temperature insulating brick, a common ceramic pipe, a carbon fiber composite heat insulation plate, a carbon fiber composite heat insulation graphite pipe, a graphite lining and a graphite heating body from outside to inside.

The vacuum gasification tunnel kiln introduces clean mixed gas stored in a gas storage tank through a pipeline for heat energy transfer.

Compared with the prior art, the invention mainly has the following remarkable advantages:

1. the invention completely recycles the reed and the oil sludge, and converts the useful components in the waste into single substances or simple mixtures with high added values. The reed comprises the following main components in percentage by weight: 6.8 percent of protein, 2.1 percent of fat, 34.5 percent of nitrogen-free extract, 53.3 percent of crude fiber, 5.3 to 6.8 percent of ash and trace sulfide and nitride, wherein the ash is P₂O₅ 、K₂O, CaO are provided. The content of inorganic matters in the oil sludge is 5 to 15 percent, and the oil sludge contains Al₂O₃ 、SiO₂ 、CaO、MgO、Na₂O、K₂O、Fe₂O₃、ZnO、TiO₂、ZrO₂Sulfides, nitrides and the like; the organic matter content is 5% -50%, and it contains benzene series, phenols, anthracene, pyrene, etc., and the water content and various chemical additives content is 25% -90%.

2. The reed and the oil sludge are carbonized and cracked at high temperature to generate C_nH_n、CO、H₂、N₂And the gas is collected and stored to become energy gas with high added value.

3. Residual carbon generated by high-temperature carbonization and cracking of the reed and the oil sludge reacts with inorganic matters in the oil sludge, metal magnesium, metal zinc, metal calcium, metal aluminum, metal iron, metal sodium, metal potassium and the like volatilize in a steam form under a high-temperature vacuum atmosphere, and silicon element is converted into high-temperature-resistant silicon carbide. According to the measurement, calcium element, aluminum element and the like are vaporized and volatilized at the temperature of over 1800 ℃; the metal elements of potassium and sodium are vaporized and volatilized before 1100-1400 ℃; the silicon element is transformed into a silicon carbide crystal phase at a temperature of more than 1600 ℃; reducing iron element into simple substance iron at high temperature, volatilizing iron atoms at high temperature, and crystallizing at about 1000 deg.C in cooling process; partial sulfide and phosphide generate elemental sulfur and elemental phosphorus at high temperature respectively, and the elemental sulfur and the elemental phosphorus are volatilized and crystallized.

4. The clean mixed gas stored in the gas storage tank is sent to a power plant for power generation, one part of the clean mixed gas is supplied to the process of the gas storage tank, and the rest part of the clean mixed gas is merged into a power grid.

5. The waste heat is fully utilized. The waste heat of the clean mixed gas stored in the gas storage tank is transferred to the materials in the preheating zone and the kiln car through heat to be heated, and the residual waste heat is sent to a material drying chamber and a warm water aquaculture plant to be heated and is used for heating users.

6. The invention has wide technical application range. The technology can be applied to any waste treatment, such as red mud, industrial garbage, household garbage, urban sludge, various slags and the like.

Drawings

FIG. 1 is a schematic view of the structural layout of the present invention;

FIG. 2 is a schematic structural view of a preheating zone (or cooling zone) of the vacuum gasification tunnel kiln of the present invention;

FIG. 3 is a schematic structural view of a high temperature zone of the vacuum gasification tunnel kiln of the present invention;

FIG. 4(a) is an XRD spectrum of the residue after decomposition of oil sand at 1900 ℃ under 1500-;

FIG. 4(b) is the XRD spectrum of the residue after the oil sand is decomposed at 1500 ℃ and 1000-;

FIG. 5(a) is an XRD spectrum of the residue after decomposition of CaO in oil sand at 1900 ℃ under 1500-;

FIG. 5(b) is an XRD spectrum of the residue after decomposition of CaO in oil sand at 1500 ℃ and 1000-;

FIG. 6(a) shows SiO in oil sand₂XRD pattern of residue after decomposition at 1500-;

FIG. 6(b) shows SiO in oil sand₂XRD pattern of residue after decomposition at 1000-;

FIG. 7(a) shows Al in oil sand₂O₃XRD pattern of residue after decomposition at 1500-;

FIG. 7(b) shows Al in oil sand₂O₃XRD pattern of residue after decomposition at 1000-;

FIG. 8 shows K in oil sludge sand₂CO₃XRD pattern of residue after 1100-;

FIG. 9 shows Na in oil-containing silt₂CO₃XRD pattern of residue after 1100-;

in the figure: 1-raw material workshop, 2-track turnover vehicle, 3-oil sludge-reed brick kiln vehicle, 4-first automatic opening door, 5-feeding vacuum chamber, 6-second automatic opening door, 7-low temperature zone condensation tank, 8-medium temperature zone condensation tank, 9-gas channel, 10-gas storage tank, 11-high temperature zone condensation tank, 12-third automatic opening door, 13-discharging vacuum chamber, 14-fourth automatic opening door, 15-vacuum gasification tunnel kiln, 16-discharge workshop, 17-metal shell, 18-low temperature felt, 19-high temperature insulating brick, 20-common ceramic pipe, 21-carbon fiber composite insulating board, 22-carbon fiber composite insulating graphite pipe, 23-carbon fiber composite insulating graphite board, 24-graphite lining, 25-graphite heating element, 26-rail.

Detailed Description

The present invention will be described in detail below with reference to the following examples and accompanying drawings.

Example 1

See fig. 1, 2 and 3. A method for resource utilization of oil sludge-reed comprises the following steps:

(1) drying the reed at 100 ℃, and rolling and preparing into reed powder with the particle size less than 1 mm.

(2) Mixing oil sludge: the reed powder is uniformly mixed according to the weight ratio of 1:0.5, and then the mixture is pressed into an oil sludge-reed brick with the length of 240mm, the width of 120mm and the thickness of 60 mm.

(3) The oil sludge-reed bricks are sent into a vacuum gasification tunnel kiln 15 through an oil sludge-reed brick kiln car 3, and are gradually heated from room temperature to 1900 ℃ by adopting electric energy, so that water and organic matters in the oil sludge are gasified, decomposed and carbonized, and are mixed with oxides in the oil sludge,The sulfide and the nitride are subjected to reduction and carbonization reactions. The chemical change of the components contained in the reed is as follows: protein, fat, nitrogen-free extract, C of cracking crude fiber into small molecules_nH_n、CO、H₂、N₂C, P₂O₅ 、K₂Gasifying O at high temperature, reacting CaO and charcoal to generate calcium carbide and CO, generating elemental S from sulfur in sulfide, and generating N from nitrogen in nitride₂. The chemical change of the components contained in the oil sludge is as follows: cracking organic matter into small molecule C_nH_n、CO、H₂、N₂Carbon, Al₂O₃Reacting with C under reducing atmosphere to generate Al₄C₃And CO gas, SiO₂Reacting with C to generate SiC and CO gas, reacting CaO with C to generate CaC₂And CO, MgO reacts with C to generate metal Mg, CO and Na₂O and K₂Gasifying O at high temperature, reacting ZnO with C to generate Zn, CO and Fe₂O₃React with C to generate Fe, CO and TiO₂React with C to produce TiC and CO gas, ZrO₂Reacting with C to generate ZrC and CO, generating S from sulfur in sulfide and N from nitrogen in nitride₂。

(4) And (4) leading out the gas obtained in the step (3) from low to high in a segmented manner, and respectively condensing or crystallizing single substances with high purity and high added value in a condensation tank of a corresponding temperature section according to the liquefaction temperature point or the crystallization temperature point of different gas types. Small molecule C generated by cracking_nH_nCondensing and separating in a low-temperature zone condensing tank 7, and gasifying P at high temperature₂O₅ 、K₂O、Na₂O, S condensing and crystallizing in the middle temperature zone condensing tank 8, condensing and crystallizing in the high temperature zone condensing tank 11 for separating Mg vapor and Zn vapor, and separating CO and H₂、 N₂Sent to a gas storage tank 10 through a gas passage 9 for storage.

(5) And (4) gradually cooling and discharging the carbide and the surplus carbon generated in the step (3) at the tail part of the vacuum gasification tunnel kiln 15, and further processing. Separating the generated metal Fe by a magnetic separator; mixing Al₄C₃、SiC、CaC₂TiC, ZrC and water, wherein Al₄C₃、CaC₂Reaction with water to form Al (OH)₃ 、Ca（OH）₂ And acetylene gas, and collecting and storing the obtained acetylene gas; SiC, TiC, ZrC and the like cannot react with water; the obtained Al (OH)₃ 、Ca（OH）₂Rinsing the mixture of SiC, TiC, ZrC and residual C with water, and separating into two groups of high value-added mixtures, wherein one group is Al (OH)₃ 、Ca（OH）₂And C, and the other group is a mixture of SiC, TiC and ZrC.

Example 2

See fig. 1, 2 and 3. A method for resource utilization of oil sludge-reed comprises the following steps:

(1) drying the reed at 120 ℃, and rolling and preparing into reed powder with the particle size less than 1 mm.

(2) Mixing oil sludge: the reed powder is uniformly mixed according to the weight ratio of 1:1, and then the mixture is pressed into an oil sludge-reed brick with the length of 240mm, the width of 120mm and the thickness of 60 mm.

(3) The oil sludge-reed bricks are sent into a vacuum gasification tunnel kiln 15 through an oil sludge-reed brick kiln car 3, and are gradually heated to 1900 ℃ from room temperature by adopting electric energy, so that water and organic matters in the oil sludge are gasified, decomposed and carbonized, and are subjected to reduction and carbonization reactions with oxides, sulfides and nitrides in the oil sludge. The chemical change of the components contained in the reed is as follows: protein, fat, nitrogen-free extract, C of cracking crude fiber into small molecules_nH_n、CO、H₂、N₂C, P₂O₅ 、K₂Gasifying O at high temperature, reacting CaO and charcoal to generate calcium carbide and CO, generating elemental S from sulfur in sulfide, and generating N from nitrogen in nitride₂. The chemical change of the components contained in the oil sludge is as follows: cracking organic matter into small molecule C_nH_n、CO、H₂、N₂Carbon, Al₂O₃Reacting with C under reducing atmosphere to generate Al₄C₃And CO gas, SiO₂Reacting with C to generate SiC and CO gas, reacting CaO with C to generate CaC₂And CO, MgO reacts with C to generate metal Mg, CO and Na₂O and K₂Gasifying O at high temperature, reacting ZnO with C to generate Zn, CO and Fe₂O₃React with C to generate Fe, CO and TiO₂React with C to produce TiC and CO gas, ZrO₂Reacting with C to generate ZrC and CO, generating S from sulfur in sulfide and N from nitrogen in nitride₂。

(4) And (4) leading out the gas obtained in the step (3) from low to high in a segmented manner, and respectively condensing or crystallizing single substances with high purity and high added value in a condensation tank of a corresponding temperature section according to the liquefaction temperature point or the crystallization temperature point of different gas types. Small molecule C generated by cracking_nH_nCondensing and separating in a low-temperature zone condensing tank 7, and gasifying P at high temperature₂O₅ 、K₂O、Na₂O, S condensing and crystallizing in the middle temperature zone condensing tank 8, condensing and crystallizing in the high temperature zone condensing tank 11 for separating Mg vapor and Zn vapor, and separating CO and H₂、 N₂Sent to a gas storage tank 10 through a gas passage 9 for storage.

(5) And (4) gradually cooling and discharging the carbide and the surplus carbon generated in the step (3) at the tail part of the vacuum gasification tunnel kiln, and further processing. Separating the generated metal Fe by a magnetic separator; mixing Al₄C₃、SiC、CaC₂TiC, ZrC and water, wherein Al₄C₃、CaC₂Reaction with water to form Al (OH)₃ 、Ca（OH）₂ And acetylene gas, and collecting and storing the obtained acetylene gas; SiC, TiC, ZrC and the like cannot react with water; the obtained Al (OH)₃ 、Ca（OH）₂Rinsing the mixture of SiC, TiC, ZrC and residual C with water, and separating into two groups of high value-added mixtures, wherein one group is Al (OH)₃ 、Ca（OH）₂And C, and the other group is a mixture of SiC, TiC and ZrC.

Example 3

See fig. 1, 2 and 3. A method for resource utilization of oil sludge-reed comprises the following steps:

(1) drying the reed at 150 ℃, and rolling and preparing into reed powder with the particle size of less than 1 mm.

(2) Mixing oil sludge: the reed powder is uniformly mixed according to the weight ratio of 1:1.5, and then the mixture is pressed into an oil sludge-reed brick with the length of 240mm, the width of 120mm and the thickness of 60 mm.

(3) The oil sludge-reed bricks are sent into a vacuum gasification tunnel kiln 15 through an oil sludge-reed brick kiln car 3, and are gradually heated to 1900 ℃ from room temperature by adopting electric energy, so that water and organic matters in the oil sludge are gasified, decomposed and carbonized, and are subjected to reduction and carbonization reactions with oxides, sulfides and nitrides in the oil sludge. The chemical change of the components contained in the reed is as follows: protein, fat, nitrogen-free extract, C of cracking crude fiber into small molecules_nH_n、CO、H₂、N₂C, P₂O₅ 、K₂Gasifying O at high temperature, reacting CaO and charcoal to generate calcium carbide and CO, generating elemental S from sulfur in sulfide, and generating N from nitrogen in nitride₂. The chemical change of the components contained in the oil sludge is as follows: cracking organic matter into small molecule C_nH_n、CO、H₂、N₂Carbon, Al₂O₃Reacting with C under reducing atmosphere to generate Al₄C₃And CO gas, SiO₂Reacting with C to generate SiC and CO gas, reacting CaO with C to generate CaC₂And CO, MgO reacts with C to generate metal Mg, CO and Na₂O and K₂Gasifying O at high temperature, reacting ZnO with C to generate Zn, CO and Fe₂O₃React with C to generate Fe, CO and TiO₂React with C to produce TiC and CO gas, ZrO₂Reacting with C to generate ZrC and CO, generating S from sulfur in sulfide and N from nitrogen in nitride₂。

(4) And (4) leading out the gas obtained in the step (3) from low to high in a segmented manner, and respectively condensing or crystallizing single substances with high purity and high added value in a condensation tank of a corresponding temperature section according to the liquefaction temperature point or the crystallization temperature point of different gas types. Small molecule C generated by cracking_nH_nCondensing and separating in a low-temperature zone condensing tank 7, and gasifying P at high temperature₂O₅ 、K₂O、Na₂O, S condensing and crystallizing in the middle temperature zone condensing tank 8, condensing and crystallizing in the high temperature zone condensing tank 11 for separating Mg vapor and Zn vapor, and separating CO and H₂、 N₂Is sent to a gas storage tank through a gas passage 910, storing.

(5) And (4) gradually cooling and discharging the carbide and the surplus carbon generated in the step (3) at the tail part of the vacuum gasification tunnel kiln, and further processing. Separating the generated metal Fe by a magnetic separator; mixing Al₄C₃、SiC、CaC₂TiC, ZrC and water, wherein Al₄C₃、CaC₂Reaction with water to form Al (OH)₃ 、Ca（OH）₂ And acetylene gas, and collecting and storing the obtained acetylene gas; SiC, TiC, ZrC and the like cannot react with water; the obtained Al (OH)₃ 、Ca（OH）₂Rinsing the mixture of SiC, TiC, ZrC and residual C with water, and separating into two groups of high value-added mixtures, wherein one group is Al (OH)₃ 、Ca（OH）₂And C, and the other group is a mixture of SiC, TiC and ZrC.

Example 4

See fig. 1, 2 and 3. An oil sludge-reed resource utilization device is matched with the oil sludge-reed resource utilization method described in the embodiment, and comprises a raw material workshop 1, an oil sludge-reed brick kiln car 3, a feeding vacuum chamber 5, a vacuum gasification tunnel kiln 15, a discharging vacuum chamber 13, a discharging workshop 16, a low-temperature area condensing tank 7, a medium-temperature area condensing tank 8, a high-temperature area condensing tank 11, an air storage tank 10 and an air channel 9. The raw material workshop 1, the feeding vacuum chamber 5, the vacuum gasification tunnel kiln 15, the discharging vacuum chamber 13 and the discharging workshop 16 are sequentially communicated and are conveyed through the oil sludge-reed brick kiln car 3 on the track 26. The vacuum gasification tunnel kiln 15 includes a preheating zone, a high temperature zone, and a cooling zone. The low-temperature-region condensing tank 7, the medium-temperature-region condensing tank 8 and the high-temperature-region condensing tank 11 are arranged in a matching way and distributed on the outer side of the vacuum gasification tunnel kiln 15. The gas storage tank 10 is respectively connected with the low-temperature region condensing tank 7, the medium-temperature region condensing tank 8 and the high-temperature region condensing tank 11 through a gas channel 9.

Example 5

See fig. 1, 2 and 3. An oil sludge-reed resource utilization device is characterized in that two sets of a low-temperature region condensation tank 7, a medium-temperature region condensation tank 8 and a high-temperature region condensation tank 11 are arranged on the basis of the technical scheme recorded in embodiment 4 and are respectively arranged on the left side and the right side of a vacuum gasification tunnel kiln 15; one set is operated during production, and the other set is unloaded or reserved.

Example 6

See fig. 1, 2 and 3. An oil sludge-reed resource utilization device is characterized in that on the basis of the technical scheme recorded in embodiment 4, a preheating zone and a cooling zone of a vacuum gasification tunnel kiln 15 are identical in structure, and the kiln wall of the vacuum gasification tunnel kiln is sequentially provided with a metal shell 17, a low-temperature felt 18, a high-temperature insulating brick 19, a common ceramic tube 20, a carbon fiber composite heat-insulating plate 21, a carbon fiber composite heat-insulating graphite tube 22, a carbon fiber composite heat-insulating graphite plate 23 and a graphite lining 24 from outside to inside; the kiln wall of the high-temperature zone is sequentially provided with a metal shell 17, a low-temperature felt 18, a high-temperature insulating brick 19, a common ceramic tube 20, a carbon fiber composite heat insulating plate 21, a carbon fiber composite heat insulating graphite tube 22, a graphite lining 24 and a graphite heating body 25 from outside to inside.

In order to investigate in detail various chemical changes caused by the mixture of the oil sludge sand and the reed during the calcination process at 1900 ℃ under 1000-.

As can be seen from fig. 4: the mixture of the oil sludge sand and the reed is calcined at the temperature of 1000-1900 ℃. In the temperature of 1500 ℃ of 1000-₂(ii) a With increasing temperature, SiC and SiO₂The diffraction peaks gradually became higher and narrower, indicating that the crystal grain size became larger as the crystallinity was better. When the calcination temperature is raised from 1500 ℃ to 1900 ℃, SiO is heated to 1600 DEG C₂The crystal phase is completely converted to SiC. The main crystal phases of the final sample were β -SiC (PDF #75-0254, Cubic), α -SiC (PDF #31-1232, Hexagonal), and Fe_0.94O (PDF #79-1970), and the diffraction peak becomes higher and narrower as the temperature increases.

As can be seen from fig. 5: the C + CaO is calcined at 1900 ℃ under 1000-DEG C. 1000-1500 ℃, the main crystal phase is CaO, and the diffraction peak of CaO becomes lower and wider with the temperature rise, which indicates that the generation reaction of CaO is continuously reduced. When the calcination temperature is increased from 1500 ℃ to 1900 ℃, the diffraction peak of CaO disappears at 1600 ℃, and a large amount of Ca (OH) appears₂Diffraction peak of (1), here Ca (OH)₂Is due to CaC₂Caused by deliquescence, CaC₂Contact with air is rapidly deliquesced. CaC appeared at 1700 deg.C₂The diffraction peak of (a) is,CaC above 1800 DEG C₂The diffraction peak disappears, and Ca element is vaporized and volatilized. The main crystal phase of the final sample was C, and as the temperature increased, the diffraction peak became higher and narrower.

As can be seen from fig. 6: c + SiO₂Calcining at 1900 ℃ at 1000-temperature. An orthogonal SiO in the vicinity of 2 theta =28 DEG at 1500 ℃ of 1000-₂The conversion to SiC was complete at 1300 ℃ and a diffraction peak of SiC appeared at 1400 ℃. When the calcining temperature is 1500-1900 deg.C, and is 1600 deg.C, SiO₂The crystal phase was completely converted to SiC, the main crystal phases of the final sample were C and SiC, and the diffraction peak became high and narrow as the temperature increased.

As can be seen from fig. 7: c + Al₂O₃Calcining at 1900 ℃ at 1000-temperature. At the temperature of 1000 ℃ and 1500 ℃, Al₂O₃No reaction. When the calcining temperature is increased from 1500 ℃ to 1900 ℃, Al is generated by reaction with C at 1700 DEG C₄C₃Al at 1800 DEG C₄C₃Al and C are formed by decomposition, finally Al atoms volatilize, the main crystal phase of the final sample is C, and the diffraction peak becomes higher and narrower with the increase of the temperature.

As can be seen from fig. 8: c + K₂CO₃Calcining at 1100-1400 deg.C. The sample had a main crystal phase of C, no diffraction peak of K element was detected, and K was found in the unfired sample₂CO₃Diffraction peak of (2), Explanation K₂CO₃Completely decomposed at a temperature below 1100 ℃ and volatilized out.

As can be seen from fig. 9: c + Na₂CO₃Calcining at 1100-1400 deg.C. The sample had a main crystal phase of C, and Na was not detected₂CO₃Diffraction peak of (1), and Na in the unfired sample₂CO₃The diffraction peak of (1). Description of Na₂CO₃Completely decomposed at a temperature below 1100 ℃ and volatilized out.

To sum up the above conclusions, the mixed pyrolysis of oil sludge sand and reed is feasible under the high-temperature vacuum atmosphere, most of the metal elements can be vaporized and volatilized, and the specific reaction process is as follows:

ca element:finally, Ca atom is vaporized and volatilizedHair is sent;

si element:because SiC is high-temperature resistant, the SiC is finally left in the sample;

al element: ，finally, evaporating and volatilizing Al atoms;

K. na metal element completes the reaction before 1100-1400 ℃, and the specific temperature cannot be determined due to vaporization and volatilization.

The experiment confirms the temperature stages of metal vaporization in the pyrolysis oil sludge sand, can collect metal element vaporization gas at different temperature stages, provides powerful experimental basis for designing a high-temperature kiln, and makes further contribution to the realization of harmless and recycling treatment of the oil sludge sand.