阅读说明：本技术 一种均相加氢处理高盐高氯餐厨废油的方法 (Method for homogeneous phase hydrogenation treatment of high-salt high-chlorine kitchen waste oil ) 是由 陈松 王康县 李广慈 荣磊 李学兵 王�忠 范芮堃 周剑伟 于 2020-11-23 设计创作，主要内容包括：本发明公开了一种均相加氢处理高盐高氯餐厨废油的方法,其可实现高盐高氯餐厨废油处理连续长期运转,且可以很好的脱除高盐高氯餐厨废油金属盐类及氯等杂质,尤其对高盐高氯餐厨废油中氯脱除有了更明确的方法,为高盐高氯餐厨废油后续处理装置保驾护航。(The invention discloses a method for homogeneous phase hydrogenation treatment of high-salt high-chlorine kitchen waste oil, which can realize continuous long-term operation of high-salt high-chlorine kitchen waste oil treatment, can well remove impurities such as metal salts and chlorine in the high-salt high-chlorine kitchen waste oil, particularly has a more definite method for removing chlorine in the high-salt high-chlorine kitchen waste oil, and protects driving and navigation for a subsequent treatment device of the high-salt high-chlorine kitchen waste oil.)

1. A method for homogeneous phase hydrogenation treatment of high-salt high-chlorine kitchen waste oil comprises a method of coupling homogeneous phase hydrogenation and hydrodechlorination by adopting a liquid catalyst characteristic.

2. The method for homogeneous hydrogenation treatment of high-salt high-chlorine kitchen waste oil according to claim 1, wherein the high-salt high-chlorine kitchen waste oil is subjected to homogeneous hydrogenation reaction in a hydrogen state at a certain temperature, and a hot high-molecular gas phase is subjected to hydrodechlorination refining and dechlorination adsorption reaction, and the method comprises the following steps: (A) high-salt high-chlorine kitchen waste oil hydrogenation reaction: introducing high-salt high-chlorine kitchen waste oil into a low-pressure homogeneous phase hydrogenation reactor; (B) hydrogenation and dechlorination of high-salt high-chlorine kitchen waste oil: the hot high-molecular gas phase enters a hydrogenation dechlorination refining reactor and a dechlorination adsorption reactor; (C) separating the residual liquid of the high-salt and high-chlorine kitchen waste oil: the hot high-separation liquid phase is decompressed and then enters a residual liquid separation system (a decompression tower or a centrifuge), and the product after deslagging and the dechlorinated product are mixed directly or are refined after supplement to obtain a finished product.

3. The method as claimed in claim 1, wherein the pressure of the low-pressure homogeneous hydrogenation system in the hydrogen state is 2.0-8.0MPa, the temperature of the homogeneous hydrogenation is 220-420 ℃, and the hydrogenation reaction is carried out in the liquid catalyst environment.

4. The method as claimed in claim 1, wherein the hydrodechlorination system has a hydrogen pressure of 1.0-8.0MPa, and the hydrodechlorination temperature is 150-360 ℃, preferably 260-320 ℃.

5. The method for homogeneous hydrogenation treatment of high-salt high-chlorine kitchen waste oil as claimed in claim 1, wherein the high-chlorine kitchen waste oil comprises waste oil, hogwash oil or mixture of waste oil and hogwash oil from kitchen waste and catering recovery process.

6. The method for homogeneous hydrogenation treatment of high-salt high-chlorine kitchen waste oil according to claim 1, characterized in that the thermal high-molecular gas phase hydrogenation dechlorination process is characterized in that two dechlorination adsorption reactors which can be switched in parallel or in series are connected in series after the hydrodechlorination reactor.

7. The method according to claim 1, wherein the high-salt high-chlorine kitchen waste oil is a chlorine-containing high-salt high-chlorine kitchen waste oil, and the hydrodechlorination refining reaction and the dechlorination adsorption reaction are performed in a hydrodechlorination refining reactor (7) and a dechlorination adsorption reactor (8), wherein the dechlorination refining reactor is filled with a hydrodechlorination refining catalyst and the dechlorination adsorption reactor is filled with a dechlorination adsorption catalyst.

8. The method for homogeneous hydrotreatment of high-salt high-chlorine kitchen waste oil as claimed in claim 1, wherein the high-salt high-chlorine kitchen waste oil has a chlorine content generally not less than 10ppm, usually more than 20 ppm.

9. The method for homogeneous hydrogenation treatment of high-salt high-chlorine kitchen waste oil as claimed in claim 1, characterized in that the finished product is a long-carbon paraffin-rich material.

Technical Field

The invention belongs to the technical field of hazardous waste resource recycling and environmental protection, and relates to a method for homogeneous phase hydrogenation treatment of high-salt high-chlorine kitchen waste oil.

Background

High-salt high-chlorine kitchen waste oil generally refers to various inferior oils in life, such as recycled edible oil, repeatedly used frying oil and the like. The appearance of kitchen waste oil not only can cause the pollution to the environment on the one hand, and on the other hand still probably has the kitchen waste oil backward flow dining table to cause serious food and drink potential safety hazard. The high-salt high-chlorine kitchen waste oil has wide grease sources, but the quality of the high-salt high-chlorine kitchen waste oil is difficult to control, the high-salt high-chlorine kitchen waste oil has complex components and various varieties, and the fixed bed hydrotreatment cannot be directly carried out. For example, the high-salt high-chlorine kitchen waste oil also contains a large amount of metal salts and chlorine, which can cause poisoning or scaling of a hydrogenation catalyst in a fixed bed hydrogenation process, so that the salts and the chlorine in the high-salt high-chlorine kitchen waste oil need to be removed as much as possible by some pretreatment methods before hydrogenation so as to improve the production continuity. The waste cooking oil and the like are used as raw materials and are prepared by ester exchange or esterification reaction with lower alcohol.

In the conventional preparation process, concentrated sulfuric acid is often used as a catalyst. Although the concentrated sulfuric acid has high catalytic activity, the method has the defects of easy side reaction, difficult purification of products, serious equipment corrosion, serious environmental pollution and the like, and the process route does not meet the requirements of sustainable development of the current society. The catalyst adopts solid acid, metal salts, ionic liquid and the like, and although some defects of the traditional catalyst are solved to a certain extent, the catalyst still has the defects of low relative activity, easy carbon deposition on the surface, uneven distribution of acid centers, difficult regeneration and the like, thereby limiting the application of the catalyst.

CN102464998B relates to a method for producing high-quality diesel oil by catalytic hydrogenation of animal and vegetable oil and CN103374405B relates to a hydrogenation combination method for producing high-quality low-freezing-point diesel oil by biological oil, wherein a biomass oil raw material is mixed with hydrogen and then enters a solid catalyst fixed bed reactor for hydrogenation reaction, and the method adopts a solid catalyst fixed bed reactor for hydrogenation in the first stage, so that the lipid, unsaturated hydrocarbon, oxygen-containing hydrocarbon, especially metal salt, chlorine and the like in the animal and vegetable oil can corrode and block pipelines and equipment, thereby causing potential safety hazard and frequent shutdown of the device.

CN102911696B relates to a hydrogenation method for producing motor fuel by biological oil, the biological oil and hydrogen are mixed and then enter a solid catalyst fixed bed reactor for hydrogenation reaction, the hydrogenation is also a solid catalyst fixed bed reactor, no facility specially aiming at treating metal salts and chlorine is provided, and pipelines and equipment are corroded and blocked, so that potential safety hazards and frequent shutdown of the device are caused.

Aiming at the problems, the inventor carries out a great deal of experimental research on the treatment of the high-salt high-chlorine kitchen waste oil, and particularly invents a method for treating the high-salt high-chlorine kitchen waste oil by homogeneous phase hydrogenation.

Disclosure of Invention

In order to solve the problems, the invention provides a method for homogeneous phase hydrogenation treatment of high-salt high-chlorine kitchen waste oil, which comprises the following steps: the method comprises the following specific steps:

(1) homogeneous hydrogenation of high-salt high-chlorine kitchen waste oil: the high-salt high-chlorine kitchen waste oil with the temperature of 50 ℃ from a tank area is pressurized to 2.0-8.0Mpa by a feed pump (1), then mixed with hydrogen to enter a mixer (2), then enters a feed heat exchanger (3) to exchange heat with a hydrodechlorination reaction product to 100-300 ℃, then enters a feed heating furnace (4) to be heated to 220-420 ℃, mixed with a liquid catalyst to enter a homogeneous reactor (5), the reaction temperature is 220-420 ℃, and the pressure is 2.0-8.0 Mpa; the liquid catalyst is placed in a catalyst tank (11).

(2) Hydrogenation and dechlorination of high-salt high-chlorine kitchen waste oil: the homogeneous reaction product enters a thermal high-pressure separator (6) for gas-liquid phase separation, the gas phase at the top of the thermal high-pressure separator (6) enters a hydrodechlorination refining reactor (7) and a dechlorination adsorption reactor (8) for hydrodechlorination refining reaction and dechlorination adsorption reaction, the hydrodechlorination refining reactor is provided with a hydrodechlorination refining catalyst, the dechlorination adsorption reactor is provided with a dechlorination adsorption catalyst, the hydrodechlorination refining reaction temperature is 150-360 ℃, the pressure is 1.0-8.0MPa, and the volume space velocity is: 0.1-10.0 h-1; the dechlorination adsorption reaction temperature is 150-: 0.1-10.0 h-1; feeding the hydrodechlorination refined reaction product into a feeding heat exchanger (3) to exchange heat with a high-salt high-chlorine kitchen waste oil raw material, heating the raw material to 100-300 ℃, cooling the hydrodechlorination refined reaction product to 180-280 ℃, then feeding the hydrodechlorination refined reaction product into an air cooler (12) to be cooled to 40-60 ℃, separating dechlorinated light oil, circulating gas and low-pressure gas from the product in a cold high-pressure separator (13) and a low-pressure separator (14), feeding circulating hydrogen at the top of the cold high-pressure separator (13) into a circulating hydrogen compressor (15) to be pressurized, and then mixing the pressurized circulating hydrogen with the high-salt high-chlorine kitchen waste oil raw material; the separation temperature of the cold high-pressure separator (13) is 40-60 ℃, and the pressure is 1.0-8.0 Mpa; the low-pressure separator (14) has a separation temperature of 40-60 deg.C and a pressure of 0.1-3.0 MPa.

(3) Fractionating high-salt high-chlorine kitchen waste oil: the liquid phase at the bottom of the hot high-pressure separator (6) enters the hot low-pressure separator (9) for gas-liquid phase separation through decompression, the separation temperature of the hot low-pressure separator (9) is 220-; the liquid at the bottom of the hot low-pressure separator (9) enters a residual liquid separation system, and a product obtained after deslagging in the residual liquid separation system (a decompression tower or a centrifugal machine) is mixed with the dechlorinated product directly or is refined after supplement to obtain a finished product.

The method has the advantages that the continuous long-term operation of the treatment of the high-salt high-chlorine kitchen waste oil can be realized, impurities such as metal salts, chlorine and the like in the high-salt high-chlorine kitchen waste oil can be well removed, particularly, a more definite method is provided for removing the chlorine in the high-salt high-chlorine kitchen waste oil, and the method is used for protecting driving and navigation of a subsequent treatment device of the high-salt high-chlorine kitchen waste oil. And this step can be with high salt high chlorine kitchen waste oil fixed bed hydrofining supporting, can guarantee that high salt high chlorine kitchen waste oil treatment part moves in succession and guarantees that follow-up fixed bed hydrofining equipment does not receive chlorine corruption, prevents cold equipment of trading and blocks up, increases the safety of kitchen waste oil processing apparatus operation, environmental protection and the reliability of long period.

Drawings

FIG. 1 is a process flow diagram of the steps of the homogeneous phase hydrogenation treatment method of high-salt high-chlorine kitchen waste oil.

In the figure, 1 is a feed pump, 2 is a mixer, 3 is a feed heat exchanger, 4 is a feed heating furnace, 5 is a homogeneous reactor, 6 is a hot high-pressure separator, 7 is a hydrodechlorination refining reactor, 8 is a dechlorination adsorption reactor, 9 is a hot low-pressure separator, 10 is a raffinate separation system, 11 is a catalyst tank, 12 is an air cooler, 13 is a cold high-pressure separator, 14 is a low-pressure separator, and 15 is a recycle hydrogen compressor.

Detailed Description

The basic principle of the method for the homogeneous phase hydrogenation treatment of the high-salt high-chlorine kitchen waste oil is as follows:

the high-salt high-chlorine kitchen waste oil is mixed with hydrogen under the low-pressure working condition and is subjected to hydrogenation reaction under the action of a liquid catalyst, metal salts, chlorine, oxygen-containing compounds and other substances which are easy to coke in the high-salt high-chlorine kitchen waste oil can be decomposed by the reaction, in addition, the chlorine in the high-salt high-chlorine kitchen waste oil exists in an organic chlorine mode, the organic chlorine cannot be reacted by a dechlorination adsorption catalyst, therefore, the organic chlorine hydrofining reaction in the high-salt high-chlorine kitchen waste oil needs to be changed into inorganic chlorine, the inorganic chlorine can react with the dechlorination adsorption catalyst, the chlorine in the high-salt high-chlorine kitchen waste oil is removed, and the substances such as lipids, unsaturated hydrocarbons, oxygen-containing hydrocarbons and the like in the high-salt high-chlorine kitchen waste oil can be subjected to hydrogenation saturation and.

The invention will be described in detail below with reference to the accompanying figure 1 and the detailed description, but the invention is not limited to the example description

The first embodiment is as follows:

mixing high-salt high-chlorine kitchen waste oil with circulating hydrogen at an outlet of a circulating hydrogen compressor 14 through a feeding pump 1, feeding the mixture into a mixer 2, feeding the uniformly mixed raw material into a raw material heat exchanger 3 to exchange heat with a hydrodechlorination refined reaction product, feeding the raw material into a feeding heating furnace 4 after the heat exchange is carried out to 200 ℃, heating the raw material to 320 ℃, mixing the raw material with a liquid catalyst, feeding the mixture into a homogeneous phase hydrogenation reactor 5 to carry out hydrogenation reaction, wherein the reaction temperature is 320 ℃, and the pressure is 3.0 Mpa; the reaction product from the homogeneous phase reactor 5 enters a thermal high-pressure separator 6, the gas phase at the top of the thermal high-pressure separator 6 enters a hydrodechlorination refining reaction 7 and a dechlorination adsorption reactor 8, the hydrodechlorination refining and the dechlorination adsorption reaction are carried out under the conditions of 320 ℃ and 2.5MPa, the thermal high-molecular gas phase enters a feed heat exchanger 3 after the reaction and exchanges heat with the high-salt high-chlorine kitchen waste oil raw material, the thermal high-molecular gas phase enters an air cooler 12 from 320 ℃ to 220 ℃ and is cooled to 50 ℃ and then enters a cold high-pressure separation 13 to separate out recycle hydrogen, and the recycle hydrogen is pressurized to 3.6MPa by a recycle hydrogen compressor 15 and mixed with the raw material; the liquid at the bottom of the cold high-pressure separator 13 enters a low-pressure separator 14 after being depressurized, the operating temperature of the low-pressure separator 14 is 50 ℃, the pressure is 0.7Mpa, low-fraction gas is separated and enters a downstream processing part, and low-fraction oil enters a storage tank for storage; the liquid phase at the bottom of the hot high-pressure separator 6 enters a hot low-pressure separator 9 after pressure reduction, the operating temperature of the hot low-pressure separator 9 is 320 ℃, the pressure is 0.7Mpa, the liquid phase at the bottom of the hot low-pressure separator 9 enters a residual liquid separation system 10, and the product after deslagging and the low-fraction oil of the dechlorination product are directly mixed or refined after supplement to obtain a finished product. The method completes the steps of homogeneous phase hydrogenation treatment of the high-salt high-chlorine kitchen waste oil.

Example two:

mixing high-salt high-chlorine kitchen waste oil with circulating hydrogen at an outlet of a circulating hydrogen compressor 14 through a feed pump 1, feeding the mixture into a mixer 2, feeding the uniformly mixed raw material into a raw material heat exchanger 3 to exchange heat with a hydrodechlorination refined reaction product, feeding the raw material into a feed heating furnace 4 after the temperature is changed to 260 ℃, heating the raw material to 360 ℃, mixing the raw material with a liquid catalyst, feeding the mixture into a homogeneous phase hydrogenation reactor 5 to perform hydrogenation reaction, wherein the reaction temperature is 360 ℃, and the pressure is 4.0 MPa; the reaction product from the homogeneous phase reactor 5 enters a thermal high-pressure separator 6, the gas phase at the top of the thermal high-pressure separator 6 enters a hydrodechlorination refining reaction 7 and a dechlorination adsorption reactor 8, the hydrodechlorination refining and the dechlorination adsorption reaction are carried out under the conditions of the temperature of 360 ℃ and the pressure of 3.2MPa, the thermal high-molecular gas phase enters a feed heat exchanger 3 after the reaction and exchanges heat with the high-salt high-chlorine kitchen waste oil raw material, the temperature of the thermal high-molecular gas phase is from 360 ℃ to 280 ℃, the thermal high-molecular gas phase enters an air cooler 12 and is cooled to 45 ℃, the thermal high-pressure gas phase enters a cold high-pressure separation 13 to separate the circulating hydrogen, and the circulating hydrogen is pressurized to 4.4MPa by a circulating hydrogen compressor; the liquid at the bottom of the cold high-pressure separator 13 is depressurized and enters a low-pressure separator 14, the operating temperature of the low-pressure separator 14 is 45 ℃, the pressure is 1.2Mpa, low-fraction gas is separated and enters a downstream processing part, and low-fraction oil enters a storage tank for storage; the liquid phase at the bottom of the hot high-pressure separator 6 enters a hot low-pressure separator 9 after pressure reduction, the operating temperature of the hot low-pressure separator 9 is 360 ℃, the pressure is 1.2Mpa, the liquid phase at the bottom of the hot low-pressure separator 9 enters a residual liquid separation system 10, and the product after deslagging and the low-fraction oil of the dechlorination product are directly mixed or refined after supplement to obtain a finished product. The method completes the steps of homogeneous phase hydrogenation treatment of the high-salt high-chlorine kitchen waste oil.

Comparative example one:

after the high-salt high-chlorine kitchen waste oil is subjected to the homogeneous hydrogenation treatment methods of the first embodiment and the second embodiment, the comparison conditions of the raw materials and the products are as follows:

from the first and second examples and the first and second comparative examples, the method for treating high-salt high-chlorine kitchen waste oil by adding hydrogen has obvious effect.