CN113120901B - Method for co-producing activated carbon and calcium oxide from petroleum coke and gypsum - Google Patents
Method for co-producing activated carbon and calcium oxide from petroleum coke and gypsum Download PDFInfo
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- CN113120901B CN113120901B CN201911423705.3A CN201911423705A CN113120901B CN 113120901 B CN113120901 B CN 113120901B CN 201911423705 A CN201911423705 A CN 201911423705A CN 113120901 B CN113120901 B CN 113120901B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 183
- 239000002006 petroleum coke Substances 0.000 title claims abstract description 99
- 239000010440 gypsum Substances 0.000 title claims abstract description 88
- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 80
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000000292 calcium oxide Substances 0.000 title claims abstract description 57
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 91
- 239000011593 sulfur Substances 0.000 claims abstract description 91
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 78
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 38
- 230000004913 activation Effects 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000002994 raw material Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 12
- 230000003213 activating effect Effects 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000002699 waste material Substances 0.000 abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000003546 flue gas Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0473—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by reaction of sulfur dioxide or sulfur trioxide containing gases with reducing agents other than hydrogen sulfide
- C01B17/0482—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by reaction of sulfur dioxide or sulfur trioxide containing gases with reducing agents other than hydrogen sulfide with carbon or solid carbonaceous materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/48—Sulfur dioxide; Sulfurous acid
- C01B17/50—Preparation of sulfur dioxide
- C01B17/501—Preparation of sulfur dioxide by reduction of sulfur compounds
- C01B17/506—Preparation of sulfur dioxide by reduction of sulfur compounds of calcium sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/354—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/02—Oxides or hydroxides
- C01F11/08—Oxides or hydroxides by reduction of sulfates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Carbon And Carbon Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a method for coproducing activated carbon and calcium oxide from petroleum coke and gypsum, which comprises the following steps: (1) preparing activated carbon by petroleum coke activation; (2) The petroleum coke reacts with the gas containing sulfur dioxide to generate sulfur; (3) Part of the sulfur is absorbed and impregnated on the activated carbon to prepare sulfur-rich activated carbon, and the rest of the sulfur reacts with the gypsum to generate calcium oxide and sulfur dioxide. The method for coproducing the activated carbon and the calcium oxide from the petroleum coke and the gypsum combines the utilization of the petroleum coke and the gypsum, realizes the resource and high-value utilization of the petroleum coke and the gypsum, and reduces the pollution of the high-sulfur petroleum coke and the waste gypsum to the environment.
Description
Technical Field
The invention belongs to the technical field of petroleum coke and gypsum recycling, and particularly relates to a method for preparing activated carbon and calcium oxide from petroleum coke and gypsum.
Background
The petroleum coke is a byproduct in the petrochemical industry, the main element of the petroleum coke consists of carbon, the carbon content is generally more than 80wt%, and the rest is hydrogen, oxygen, nitrogen, sulfur and metal elements, and the petroleum coke has the advantages of high carbon content, less volatile components, low ash content, high heat value and the like. Low-sulfur petroleum coke (the sulfur content is less than 3%) is mainly used as electrode coke and metallurgical coke, while high-sulfur petroleum coke (the sulfur content is more than 3%) can only be used as fuel before, but pollutants such as sulfur dioxide in flue gas can bring serious environmental pollution, and particularly newly revised atmosphere pollution prevention and control laws of the people's republic of China, executed from 2016, 1, require to establish stricter petroleum coke standards, so that the sale and utilization of high-sulfur petroleum coke are limited, and therefore, a new petroleum coke, particularly a high-sulfur petroleum coke utilization way needs to be developed, wherein the preparation of activated carbon from petroleum coke is one of ways for realizing the high-value utilization of petroleum coke.
The mercury in the coal-fired flue gas is a main source of mercury pollutants in the atmosphere, and in the existing coal-fired flue gas demercuration technology, the activated carbon adsorption demercuration is widely applied, but the problems of high activated carbon cost, low adsorption efficiency and the like still exist, so that a cheap raw material needs to be searched for developing the low-cost high-efficiency activated carbon demercuration adsorbent.
The flue gas desulfurization limestone-wet process can generate a large amount of desulfurization gypsum, a large amount of phosphogypsum is generated during the production of phosphoric acid, and the like, the industrial waste gypsum has high yield, poor quality and low utilization rate, and the accumulation of a large amount of industrial waste gypsum also brings great pressure to the environment, so that a new waste gypsum application way needs to be developed to realize resource utilization.
The patent CN105712347B discloses a method for preparing sulfur-rich activated carbon by using high-sulfur petroleum coke, potassium hydroxide activates the high-sulfur petroleum coke, and hydrogen sulfide gas is collected in the calcining process; burning high-sulfur petroleum coke to collect sulfur dioxide gas, mixing the two gases to react to generate elemental sulfur, dipping the activated carbon in elemental sulfur dipping solution, and drying to obtain sulfur-rich activated carbon. The technology generates less sulfur dioxide by burning the high-sulfur petroleum coke, needs to consume a large amount of high-sulfur petroleum coke, has higher cost, and generates a large amount of CO2 greenhouse gas by burning.
Disclosure of Invention
Aiming at the defects in the prior art, the invention mainly aims to provide a method for coproducing petroleum coke and gypsum as well as activated carbon and calcium oxide. Meanwhile, the high-value utilization of petroleum coke and gypsum is realized.
The invention provides a method for coproducing activated carbon and calcium oxide from petroleum coke and gypsum, which comprises the following steps:
(1) Contacting a gypsum raw material with a sulfur-containing material for reaction, and separating reaction products to obtain calcium oxide and sulfur dioxide gas;
(2) Enabling petroleum coke to contact with the sulfur dioxide gas obtained in the step (1) for reaction, and obtaining sulfur-containing process gas after the reaction;
(3) Mixing petroleum coke with an activating agent, activating under the nitrogen atmosphere, then washing and drying to obtain activated carbon, and finally contacting the activated carbon with the sulfur-containing process gas obtained in the step (2) to obtain the sulfur-rich activated carbon.
In the method for coproducing the activated carbon and the calcium oxide from the petroleum coke and the gypsum, the gypsum raw material in the step (1) can be one or more of natural gypsum, desulfurized gypsum and phosphogypsum, the water content of the gypsum raw material is 1-15 wt%, and the particle size of the gypsum raw material is larger than 80 meshes.
In the method for coproducing the activated carbon and the calcium oxide from the petroleum coke and the gypsum, the gypsum raw material in the step (1) is dried at the drying temperature of 80-200 ℃, preferably 100-180 ℃, and then ground and crushed to obtain a powdery material with the particle size of more than 80 meshes.
In the method for coproducing the activated carbon and the calcium oxide from the petroleum coke and the gypsum, the mass ratio of the gypsum raw material to the sulfur in the sulfur-containing material in the step (1) is 1:1 to 1:2, preferably 1:1 to 1:1.2.
in the method for coproducing the activated carbon and the calcium oxide from the petroleum coke and the gypsum, the reaction temperature in the step (1) is 800-1200 ℃, and preferably 900-1100 ℃.
In the method for coproducing the activated carbon and the calcium oxide from the petroleum coke and the gypsum, the sulfur-containing material in the step (1) is a substance containing sulfur, and can be pure sulfur or other inert components which do not react with the gypsum, and the sulfur-containing process gas obtained in the step (2) is further preferable.
In the method for coproducing the activated carbon and the calcium oxide from the petroleum coke and the gypsum, the sulfur-containing process gas obtained in the step (2) can be partially used as a sulfur-containing material to be directly returned to the step (1) for use, preferably, the sulfur-containing process gas is firstly condensed to remove gases such as carbon dioxide and the like to obtain solid sulfur, and then the solid sulfur is mixed with the gypsum raw material for reaction, so that the interference of gases such as carbon dioxide and the like can be eliminated, and the obtained relatively pure sulfur dioxide gas participates in the step (2) for reaction, and the generation of excessive carbon monoxide gas by-products is avoided.
In the method for coproducing the activated carbon and the calcium oxide from the petroleum coke and the gypsum, the petroleum coke in the step (2) and the step (3) is solid coke generated by cracking and coking vacuum residue through a coking device, and is further preferably high-sulfur petroleum coke, and the sulfur content is not less than 3wt%.
In the method for coproducing the activated carbon and the calcium oxide from the petroleum coke and the gypsum, the mass ratio of the petroleum coke in the step (2) to the sulfur dioxide gas obtained in the step (1) is 0.5 to 1, and preferably 1:1 to 5:1.
In the method for coproducing the activated carbon and the calcium oxide from the petroleum coke and the gypsum, the reaction temperature in the step (2) is 600-1000 ℃, and preferably 700-900 ℃.
In the method for coproducing activated carbon and calcium oxide from petroleum coke and gypsum, the activating agent in the step (3) is one or more of sodium hydroxide, potassium carbonate and sodium carbonate, and preferably potassium hydroxide.
In the method for co-producing the activated carbon and the calcium oxide by using the petroleum coke and the gypsum, the mass ratio of the activating agent to the petroleum coke in the step (3) is 0.5:1 to 10:1, preferably 1:1-8:1; the activation temperature is 500-1000 ℃, preferably 700-950 ℃; the activation time is 10-180 min, preferably 15-150 min
In the method for coproducing the activated carbon and the calcium oxide from the petroleum coke and the gypsum, the washing in the step (3) is carried out by using water, the washing is generally carried out for 2 to 6 times, finally, the washing and the filtering are carried out until the pH value is neutral, and the drying is carried out for 5 to 48 hours at a temperature of between 60 and 200 ℃.
In the method for coproducing the activated carbon and the calcium oxide from the petroleum coke and the gypsum, the mass ratio of the activated carbon in the step (3) to the sulfur in the sulfur-containing process gas is 30-3:1, and preferably 20.
In the method for coproducing the activated carbon and the calcium oxide from the petroleum coke and the gypsum, the temperature of the contact treatment of the activated carbon and the sulfur-containing process gas in the step (3) is 450-700 ℃, and preferably 500-650 ℃.
Compared with the prior art, the method for coproducing the activated carbon and the calcium oxide from the petroleum coke and the gypsum provided by the invention has the following advantages:
1. in the method for coproducing the activated carbon and the calcium oxide from the petroleum coke and the gypsum, the petroleum coke and the gypsum are utilized, the resource utilization and the high-value utilization of the petroleum coke and the gypsum are realized, in addition, the pollution of the high-sulfur petroleum coke and the waste gypsum to the environment is reduced, particularly when the high-sulfur petroleum coke is adopted as the raw material, the desulfurization treatment process of the high-sulfur petroleum coke raw material is saved, and the production cost of the sulfur-rich activated carbon and the calcium oxide is further reduced.
2. According to the method for coproducing the activated carbon and the calcium oxide by using the petroleum coke and the gypsum, two processes of preparing the sulfur-rich activated carbon by using the petroleum coke and producing the calcium oxide by using the waste gypsum are organically combined, the redox characteristics of sulfur dioxide and sulfur are ingeniously utilized, the calcium oxide and the sulfur dioxide are prepared by using the reaction of the waste gypsum and the sulfur, the sulfur dioxide and the petroleum coke are reacted to prepare the sulfur, the sulfur is not only a reducing agent for preparing the calcium oxide by using the waste gypsum, but also can be loaded on the activated carbon to prepare the sulfur-rich activated carbon for flue gas demercuration, and the complete utilization of resources is realized.
3. In the method for coproducing the activated carbon and the calcium oxide by using the petroleum coke and the gypsum, the petroleum coke is a carbon-based raw material for preparing the sulfur-rich activated carbon and a carbon thermal reducing agent for preparing sulfur by using sulfur dioxide, so that the utilization ways of the petroleum coke are enriched.
Detailed Description
The technical contents and effects of the present invention will be further described with reference to examples, but the present invention is not limited thereto.
The specific surface area of the activated carbon in the following examples was measured by a low-temperature nitrogen physical adsorption method using an ASAP2460 type physical adsorption apparatus from Micromeritics, under the following test conditions: the samples were vacuum treated at 80 ℃ for 5h and the testing was performed at liquid nitrogen temperature (-196 ℃). The adsorption-desorption isotherm was determined by static measurements and the specific surface area of the catalyst was calculated according to the BET (Brunauer-Emmett-Teller) equation. Sulfur loading was measured using X-ray fluorescence spectroscopy (XRF) method, test conditions: the samples were ground and tabletted, weighed, instrument parameters: target material Rh, voltage 30kV,100mA, crystal Ge, detector PC, PHA 150-300.
The demercuration performance of the petroleum coke-based sulfur-rich activated carbon prepared in the embodiment of the invention is tested on a fixed bed adsorption performance testing device. Evaluation conditions were as follows: the demercuration experiment is carried out on a fixed bed adsorption performance testing device, and the mercury concentration of an inlet of the fixed bed is 50 mg/m 3 The carrier gas is nitrogen, and the total flow of the gas is 2L/min. The particle size of the sulfur-rich activated carbon is 200-300 meshes, the loading amount is 20g, the adsorption time is 100min, and the adsorption temperature is 120 ℃. And the adsorbed gas enters an on-line flue gas mercury analyzer for analysis and determination. The following examples all employ the same evaluation conditions.
The invention provides a method for coproducing activated carbon and calcium oxide from petroleum coke and gypsum, which comprises the following steps: contacting the gypsum raw material with the sulfur-containing process gas at 800-1200 ℃ for reaction to generate calcium oxide and sulfur dioxide gas. The sulfur dioxide gas collected by separation is introduced into petroleum coke to be subjected to contact reaction at the temperature of 600-1000 ℃, and the sulfur-containing process gas is generated by the reaction. Mixing an activating agent with petroleum coke, carrying out activation reaction at 500-1000 ℃ under the condition of nitrogen atmosphere, then cooling to below 100 ℃ under the nitrogen atmosphere to obtain an activated product, washing and filtering the activated product until the pH value is neutral, and finally drying to obtain activated carbon; and (3) contacting the activated carbon with part of the process gas at 450-700 ℃, loading to obtain the sulfur-rich activated carbon, and evaluating and testing the sulfur-rich activated carbon.
In the embodiment, the gypsum raw material adopts natural gypsum, the petroleum coke adopts high-sulfur petroleum coke, and the sulfur content is 8.72%.
Example 1
The sulfur-rich activated carbon obtained by the method is marked as S-AC-1, the specific reaction conditions are shown in Table 1, and the reaction results are shown in Table 2.
Example 2
The sulfur-rich activated carbon obtained by the method is marked as S-AC-2, the specific reaction conditions are shown in table 1, and the reaction results are shown in table 2.
Example 3
The sulfur-rich activated carbon obtained by the method is marked as S-AC-3, the specific reaction conditions are shown in Table 1, and the reaction results are shown in Table 2.
Example 4
The sulfur-rich activated carbon obtained by the method is marked as S-AC-4, the specific reaction conditions are shown in table 1, and the reaction results are shown in table 2.
Example 5
The sulfur-rich activated carbon obtained by the method is marked as S-AC-5, the specific reaction conditions are shown in table 1, and the reaction results are shown in table 2.
TABLE 1 reaction conditions of examples 1 to 5
TABLE 2 Sulfur-enriched activated carbon obtained in examples 1 to 5 and its demercuration Properties
Claims (23)
1. A method for coproducing activated carbon and calcium oxide from petroleum coke and gypsum, which comprises the following steps:
(1) Contacting a gypsum raw material with a sulfur-containing material for reaction, and separating reaction products to obtain calcium oxide and sulfur dioxide gas;
(2) Contacting petroleum coke with the sulfur dioxide gas obtained in the step (1) for reaction to obtain sulfur-containing process gas after the reaction;
(3) Mixing petroleum coke with an activating agent, performing activation treatment in a nitrogen atmosphere, then performing washing and drying treatment to obtain activated carbon, and finally performing contact treatment on the activated carbon and the sulfur-containing process gas obtained in the step (2) to obtain sulfur-rich activated carbon;
the sulfur-containing process gas obtained in the step (2) is directly returned to the step (1) as a sulfur-containing material for use, the sulfur-containing process gas is condensed to obtain solid sulfur, and then the solid sulfur is mixed with a gypsum raw material for reaction;
the sulfur content of the petroleum coke in the step (2) and the step (3) is not less than 3wt%.
2. The process for co-producing activated carbon and calcium oxide from petroleum coke and gypsum as defined in claim 1, wherein: in the step (1), the water content of the gypsum raw material is 1-15 wt%, and the particle size is larger than 80 meshes.
3. The process for co-producing activated carbon and calcium oxide from petroleum coke and gypsum as defined in claim 1, wherein: in the step (1), the gypsum raw material is one or more of natural gypsum, desulfurized gypsum and phosphogypsum.
4. The process for co-producing activated carbon and calcium oxide from petroleum coke and gypsum as defined in claim 1, wherein: in the step (1), the gypsum raw material is dried at the temperature of 80-200 ℃, and then ground and crushed to obtain powdery material with the particle size larger than 80 meshes.
5. The process for co-producing activated carbon and calcium oxide from petroleum coke and gypsum as defined in claim 1, wherein: in the step (1), the quantitative ratio of the gypsum raw material to sulfur in the sulfur-containing material is 1:1 to 1:2.
6. the process for co-producing activated carbon and calcium oxide from petroleum coke and gypsum as defined in claim 5, wherein: in the step (1), the quantitative ratio of the gypsum raw material to sulfur in the sulfur-containing material is 1:1 to 1:1.2.
7. the process for co-producing activated carbon and calcium oxide from petroleum coke and gypsum as defined in claim 1, wherein: the reaction temperature in the step (1) is 800-1200 ℃.
8. The process for co-producing activated carbon and calcium oxide from petroleum coke and gypsum as claimed in claim 7, wherein: the reaction temperature in the step (1) is 900-1100 ℃.
9. The process for co-producing activated carbon and calcium oxide from petroleum coke and gypsum as defined in claim 1, wherein: the sulfur-containing material in the step (1) is a substance containing sulfur, and is pure sulfur or other inert components which do not react with gypsum.
10. The process for co-producing activated carbon and calcium oxide from petroleum coke and gypsum as claimed in claim 9, wherein: the sulfur-containing material in the step (1) is the sulfur-containing process gas obtained in the step (2).
11. The process for co-producing activated carbon and calcium oxide from petroleum coke and gypsum as defined in claim 1, wherein: the mass ratio of the petroleum coke in the step (2) to the sulfur dioxide gas obtained in the step (1) is 0.5.
12. The process for co-producing activated carbon and calcium oxide from petroleum coke and gypsum as defined in claim 11, wherein: the mass ratio of the petroleum coke in the step (2) to the sulfur dioxide gas obtained in the step (1) is 1:1-5:1.
13. The process for co-producing activated carbon and calcium oxide from petroleum coke and gypsum as defined in claim 1, wherein: the reaction temperature in the step (2) is 600-1000 ℃.
14. The process for co-producing activated carbon and calcium oxide from petroleum coke and gypsum as claimed in claim 13, wherein: the reaction temperature in the step (2) is 700-900 ℃.
15. The process for co-producing activated carbon and calcium oxide from petroleum coke and gypsum as defined in claim 1, wherein: and (3) the activating agent is one or more of sodium hydroxide, potassium carbonate and sodium carbonate.
16. The process for co-producing activated carbon and calcium oxide from petroleum coke and gypsum according to claim 15, wherein: in the step (3), the activating agent is potassium hydroxide.
17. The process for co-producing activated carbon and calcium oxide from petroleum coke and gypsum as defined in claim 1, wherein: the mass ratio of the activating agent to the petroleum coke in the step (3) is 0.5:1 to 10:1; the activation temperature is 500-1000 ℃; the activation time is 10-180 min.
18. The process for co-producing activated carbon and calcium oxide from petroleum coke and gypsum according to claim 17, wherein: the mass ratio of the activating agent to the petroleum coke in the step (3) is 1:1-8:1; the activation temperature is 700-950 ℃; the activation time is 15-150 min.
19. The process for co-producing activated carbon and calcium oxide from petroleum coke and gypsum as defined in claim 1, wherein: the drying in the step (3) is drying treatment at 60-200 ℃ for 5-48 min.
20. The process for co-producing activated carbon and calcium oxide from petroleum coke and gypsum as defined in claim 1, wherein: the mass ratio of the activated carbon in the step (3) to the sulfur in the sulfur-containing process gas is 30-3:1.
21. The process for co-producing activated carbon and calcium oxide from petroleum coke and gypsum as claimed in claim 20, wherein: the mass ratio of the activated carbon in the step (3) to the sulfur in the sulfur-containing process gas is 20-4:1.
22. The process for co-producing activated carbon and calcium oxide from petroleum coke and gypsum as defined in claim 1, wherein: the temperature of the contact treatment of the activated carbon and the sulfur-containing process gas in the step (3) is 450-700 ℃.
23. The process for co-producing activated carbon and calcium oxide from petroleum coke and gypsum according to claim 22, wherein: the temperature of the contact treatment of the activated carbon in the step (3) and the sulfur-containing process gas is 500-650 ℃.
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Effective date of registration: 20231114 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |