A kerosene co-refining method
By separating the microcomponent enrichment and catalytic depolymerization treatment, the problem of single coal species and low-quality heavy oils in the existing kerosene co-refining process is solved, and the efficiency of kerosene co-refining and product quality is improved.
Patent Information
- Application Number
- CN202310643867.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-06-01
- Publication Date
- 2025-02-14
- Estimated Expiration
- 2043-06-01
AI Technical Summary
In the existing kerosene co-refining process, single coal types and low-quality heavy oil are not suitable, resulting in low kerosene co-refining efficiency and product quality.
By macrosegregating the microcomponent enrichment from the raw coal, the microscopic group high-enriched coal samples and the inert group high-enriched coal samples were obtained, and the inert group high-enriched coal samples were subjected to catalytic depolymerization treatment. , the heavy components and low-quality heavy oil were mixed as co-refining oil, and the co-refining and hydrogenation reaction was carried out.
The optionality of coal types and oil products has been expanded, the efficiency of kerosene co-refining and product quality have been improved, especially the utilization rate of low-quality heavy oil has been significantly improved.
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Figure CN116814289B_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of fuel chemical engineering, and in particular to a kerosene co-refining method. Background Art
[0002] Co-refining of coal and oil is a new process technology developed on the basis of direct coal liquefaction technology. Compared with the technology of coal liquefaction alone, it has many advantages and realizes the coupling of modern coal chemical technology and heavy (inferior) oil processing. Co-refining of coal and oil, as a technology that integrates direct coal liquefaction and heavy oil hydrogenation, has great strategic significance in alleviating the contradiction between oil supply and demand in my country, adjusting the energy structure, and ensuring national energy security.
[0003] From the perspective of petrography, coal can be divided into vitrinite, exinite, inertinite and inorganic micro-component minerals. Different micro-components show differences in chemical structure because different coal-forming plant residues have undergone different mudification processes. The vitrinite has developed pores, high oxygen content, high hydrogen-carbon ratio, contains more saturated aliphatic hydrocarbons and hydrogen bonds, and has good hydrocarbon-forming properties; the inertinite has a high coal rank and stable structure, with high aromaticity and aromatic ring condensation, many condensed aromatic hydrocarbons, and low hydrogen content. Coal has a high added value due to its unique chemical composition and molecular structure. However, the current coal processing technology cannot fully consider the different reaction characteristics of coal micro-components, resulting in a series of problems such as low coal resource utilization.
[0004] In the kerosene co-refining process, the synergy between kerosene and coal enables kerosene co-refining to achieve a higher oil yield than direct coal liquefaction, and while ensuring the efficient conversion of coal, it also realizes the conversion and utilization of heavy oil. However, there are also some technical barriers to the kerosene co-refining process. For example, in the existing kerosene co-refining process, due to the special requirements of the structure and characteristics of the coal itself, not all coal is suitable for kerosene co-refining, and when coal from different origins is used as the raw material coal for co-refining, there are also large differences in the co-refining effect; in terms of the selection of co-refining oil, most of them choose FCC slurry oil, petroleum heavy oil or residual oil and other heavy oils with a high aromatic content, while low-quality oils or other types of heavy oils with relatively low aromatic content are not suitable as co-refining oils for the existing kerosene co-refining process.
[0005] At present, the existing process uses raw coal and heavy oil as raw materials, and adopts hydrocracking at 430-460℃ and 15-20MPa, and the overall yield is low. Therefore, it is necessary to develop a new process and method for kerosene co-refining, which can meet the adaptability of most types of coal to kerosene co-refining, and at the same time, can greatly expand the selection range of kerosene co-refining for co-refining oil, especially for the utilization of some low-quality heavy oil, and maximize the yield and quality of co-refining products.
[0006] Therefore, how to expand the selectivity of coal types and oil products suitable for kerosene co-refining, thereby improving the co-refining efficiency has become an urgent problem that technical personnel in this field need to solve. Summary of the invention
[0007] In view of this, the present invention provides a kerosene co-refining method, the purpose of which is to solve the technical problems of single coal type and unsuitability of low-quality heavy oil in the existing kerosene co-refining process.
[0008] In order to achieve the above object, the present invention adopts the following technical solution:
[0009] The present invention provides a kerosene co-refining method, comprising the following steps:
[0010] S1. Separate the maceral enrichment from the raw coal in large quantities to obtain vitrinite-rich coal samples and inertinite-rich coal samples;
[0011] S2. The inert group highly enriched coal sample is subjected to catalytic depolymerization treatment, and the product of the catalytic depolymerization treatment is divided into two parts, one part is subjected to distillation treatment to obtain heavy components; and the other part is subjected to semi-coke gasification treatment;
[0012] S3. The heavy component and the heavy oil are mixed to obtain co-refined oil, and the co-refined oil is mixed with a vitrinite high-enriched coal sample and then subjected to co-refining hydrogenation reaction to obtain a co-refining product.
[0013] Furthermore, in step S1, the raw coal is conventionally used low-rank bituminous coal or unconventionally used low-grade metamorphic coal.
[0014] Furthermore, in step S2, the specific steps of the catalytic depolymerization treatment are: spraying the catalyst solution on the inertinite-rich coal sample for catalytic depolymerization treatment; the temperature of the catalytic depolymerization treatment is 500-900° C., and the time is 0.5-3 hours.
[0015] Furthermore, the mass ratio of the mixed liquor to the inertinent highly enriched coal sample is 2 to 10:100.
[0016] Furthermore, in step S2, the heavy component is heavy oil with a boiling point ≥ 400°C.
[0017] Furthermore, in step S3, the heavy oil is one or more of low-quality FCC slurry oil, low-quality DCC slurry oil, low-quality petroleum heavy oil and low-quality residual oil.
[0018] Furthermore, in step S3, the mass ratio of the heavy component to the heavy oil is 1:1.8-2.5, and the mass ratio of the co-refined oil to the vitrinite high-enriched coal sample is 1-5:1.
[0019] Furthermore, in step S3, the hydrogen for the co-refining hydrogenation reaction comes from the raw coal gas obtained by the catalytic depolymerization treatment in step S2 and the synthesis gas obtained by the semi-coke gasification treatment.
[0020] Furthermore, in step S3, the temperature of the co-refining hydrogenation reaction is 400-500° C., the time of the co-refining hydrogenation reaction is 0.5-2 h, and the pressure of the co-refining hydrogenation reaction is 10-30 MPa.
[0021] It can be seen from the above technical solution that compared with the prior art, the beneficial effects of the present invention are as follows:
[0022] 1. The kerosene co-refining method provided by the present invention comprises the following steps: pre-fractionating the raw coal to obtain a vitrinite high-enriched coal sample and an inertinite high-enriched coal sample, and using the obtained vitrinite high-enriched coal sample as the raw material coal for kerosene co-refining, which not only increases the selectivity range of coal types for kerosene co-refining, but also ensures the conversion rate and liquid phase yield of the coal. Moreover, the product oil using the vitrinite high-enriched coal sample as the raw material coal has a high aliphatic hydrocarbon content and good oil quality;
[0023] 2. The present invention uses the tar obtained by catalytic depolymerization of the inert group high-enriched coal sample and distilled to obtain a heavy component rich in aromatics with a boiling point of 400°C or above as an oil sample, and mixes the above oil sample with low-quality heavy oil as a co-refined oil for kerosene co-refining. The two synergistically promote the hydrogenation efficiency of kerosene co-refining. After some low-quality heavy oil that does not meet the co-refining requirements is mixed with the above heavy component, its aromatic content increases significantly, meeting the requirements of kerosene co-refining for co-refining oil;
[0024] 3. The hydrogen of the present invention is entirely derived from the raw coal gas produced by catalytic depolymerization of inert group highly enriched coal samples and the synthesis gas obtained by semi-coke gasification treatment, and the catalytic depolymerization products of coal are fully utilized. BRIEF DESCRIPTION OF THE DRAWINGS
[0025] Figure 1 The present invention provides a flow chart of the kerosene co-refining method and a schematic diagram of the device, wherein 1 is a crusher, 2 is a coal grinding device, 3 is a coal sample screening device, 4 is a heavy medium cyclone, 5 is a froth flotation device, 6 is a low-rank coal catalytic depolymerization device, 7 is a semi-coke pyrolysis device, 8 is a distillation device, 9 is a PSA device, 10 is a kerosene slurry production device, and 11 is a kerosene co-refining system. DETAILED DESCRIPTION
[0026] The present invention provides a kerosene co-refining method, comprising the following steps:
[0027] S1. Separate the maceral enrichment from the raw coal in large quantities to obtain vitrinite-rich coal samples and inertinite-rich coal samples;
[0028] S2. The inert group highly enriched coal sample is subjected to catalytic depolymerization treatment, and the product of the catalytic depolymerization treatment is divided into two parts, one part is subjected to distillation treatment to obtain heavy components; and the other part is subjected to semi-coke gasification treatment;
[0029] S3. The heavy component and the heavy oil are mixed to obtain co-refined oil, and the co-refined oil is mixed with a vitrinite high-enriched coal sample and then subjected to co-refining hydrogenation reaction to obtain a co-refining product.
[0030] In the present invention, in step S1, the raw coal is conventionally used low-rank bituminous coal or unconventionally used low-grade metamorphic coal. The present invention uses lignite to represent the low-grade metamorphic coal to highlight the superiority of the present invention.
[0031] In the present invention, the specific steps of macro-separation of microscopic component enrichments are: crushing the raw coal and screening it to obtain a first coal sample and a second coal sample, placing the first coal sample in a heavy medium cyclone for sorting to obtain a vitrinite highly enriched coal sample and an inertinite highly enriched coal sample; performing froth flotation on the second coal sample to obtain a vitrinite highly enriched coal sample and an inertinite highly enriched coal sample, and then classifying the sorted and flotation products.
[0032] In the present invention, the particle size of the first coal sample is 0.2 to 2 mm, excluding 0.2 mm; the particle size of the second coal sample is 0 to 0.2 mm, including 0.2 mm.
[0033] In the present invention, the heavy medium cyclone separation is specifically as follows: the first particle size coal sample is first sent to the first heavy medium cyclone, and the separation density of the first heavy medium cyclone is 1.30-1.45 g / cm 3 The overflow is enriched with vitrinite enrichment, and the bottom flow is sent to the second heavy medium cyclone. The separation density of the second heavy medium cyclone is 1.45-1.55g / cm 3 , inertin enrichment is collected at the overflow.
[0034] In the present invention, the froth flotation agent used in the froth flotation includes a frother and a collector; the frother includes one or more of octanol, pine oil and polyethylene glycol; the collector includes one or more of kerosene, BET and diesel.
[0035] In the present invention, in step S2, the specific steps of the catalytic depolymerization treatment are: spraying the catalyst solution on the inertinite group highly enriched coal sample to perform the catalytic depolymerization treatment.
[0036] In the present invention, the temperature of the catalytic depolymerization treatment is 500-900°C, preferably 600-800°C, and more preferably 650-700°C; the time is 0.5-3h, preferably 1-2.5h, and more preferably 1.5-2h.
[0037] In the present invention, the catalyst solution comprises, by weight percentage, 0.5-1.5% potassium dichromate, 0.5-10% metal salt, 1-10% methanol, 0.05-2.0% sodium dodecylbenzene sulfonate, and the balance is water.
[0038] In the present invention, the catalyst solution is preferably 1.0% potassium dichromate, 10% metal salt, 5% methanol, 1.2% sodium dodecylbenzene sulfonate, and the balance is water; the metal salt is preferably one or more of nickel salt, iron salt, aluminum salt and zinc salt, and more preferably iron salt.
[0039] In the present invention, the mass ratio of the catalyst solution to the inertinite-rich coal sample is 2 to 10:100, preferably 3 to 8:100, and more preferably 4 to 6:100.
[0040] In the present invention, in step S2, the heavy component is heavy oil with a boiling point of ≥400°C, preferably ≥450°C, and more preferably ≥500°C.
[0041] In the present invention, in step S3, the heavy oil is one or more of low-quality FCC slurry oil, low-quality DCC slurry oil, low-quality petroleum heavy oil and low-quality residual oil, preferably one or more of low-quality FCC slurry oil, low-quality DCC slurry oil and low-quality residual oil, and further preferably low-quality FCC slurry oil and / or low-quality DCC slurry oil.
[0042] In the present invention, in step S3, the mass ratio of the heavy component to the heavy oil is 1:1.8-2.5, preferably 1:2.0-2.4, and more preferably 1:2.2-2.3; the mass ratio of the co-refined oil to the vitrinite high-enriched coal sample is 1-5:1, preferably 2-4:1, and more preferably 3:1; within the range of raw material dosage disclosed in the present invention, not only can the co-refining effect be guaranteed for the co-refining oil, but also the economy and practicality can be taken into account.
[0043] In the present invention, in step S3, the hydrogen for the co-refining hydrogenation reaction comes from the raw coal gas obtained by catalytic depolymerization treatment in step S2 and the synthesis gas obtained by semi-coke gasification treatment. The raw coal gas and the synthesis gas are treated by PSA technology to obtain hydrogen.
[0044] In the present invention, in step S3, the temperature of the co-refining hydrogenation reaction is 400-500°C, preferably 420-460°C, and more preferably 450°C; the time of the co-refining hydrogenation reaction is 0.5-2h, preferably 1-1.5h, and more preferably 1.2h; the pressure of the co-refining hydrogenation reaction is 10-30MPa, preferably 15-25MPa, and more preferably 20MPa.
[0045] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0046] Example 1
[0047] First, Xinjiang lignite was air dried and then crushed by a crusher. The particle size range of the first coal sample was determined to be 0.2-2 mm, and the particle size range of the second coal sample was determined to be 0-0.2 mm by using the process method of macro separation of microscopic component enrichment from raw coal. The first coal sample was sent to a heavy medium cyclone for sorting, and the second coal sample was sent to a froth flotation device for sorting. The vitrinite high-enrichment coal samples and inertinite high-enrichment coal samples sorted from the two sorting devices were collected. The properties of the separated high-enrichment coal samples are shown in Table 1.
[0048] The catalyst solution is sprayed on the inertin high-enriched coal sample for catalytic depolymerization treatment. The product of the catalytic depolymerization treatment is divided into two parts, one part is distilled to obtain the heavy component, and the other part is subjected to semi-coke gasification treatment; wherein the composition of the catalyst solution used is 10% ferric chloride, 5% methanol, 1.2% sodium dodecylbenzene sulfonate, and the balance is water; the parameters of the catalytic depolymerization treatment are: temperature is 650°C, and time is 0.5h.
[0049] The heavy component and low-quality FCC oil slurry were mixed in a mass ratio of 1:2 to obtain co-refined oil, wherein the composition and properties of the low-quality FCC oil slurry are shown in Table 2, and the co-refined oil and the vitrinite high-enriched coal sample were mixed in a mass ratio of 3:1 and then subjected to co-refining hydrogenation reaction to obtain the co-refining product, and the parameters of the co-refining hydrogenation reaction were: 450°C, 20MPa, 1h. The results of the co-refining hydrogenation reaction are shown in Table 3.
[0050] Table 1 Properties of coal samples
[0051]
[0052] Table 2 Composition and properties of low-quality FCC slurry oil
[0053]
[0054]
[0055] Table 3 Results of the co-refining hydrogenation reaction in Example 1
[0056] type gas(%) liquid(%) solid(%) Ash-free coal conversion rate on dry basis (%) Product yield 3.08 93.5 3.42 91.15
[0057] Example 2
[0058] The same as Example 1, except that the low-quality FCC slurry oil is replaced with low-quality DCC slurry oil, wherein the composition and properties of the low-quality DCC slurry oil are shown in Table 4, and the results of the co-refining hydrogenation reaction are shown in Table 5.
[0059] Table 4 Composition and properties of low-quality DCC slurry
[0060]
[0061] Table 5 Results of the co-refining hydrogenation reaction in Example 2
[0062] type gas(%) liquid(%) solid(%) Ash-free coal conversion rate on dry basis (%) Product yield 3.11 93.17 3.72 91.06
[0063] Comparative Example 1
[0064] The vitrinite high-enrichment coal sample obtained in Example 1 was mixed with low-quality FCC oil slurry in a mass ratio of 1:3 and then subjected to co-refining and hydrogenation reaction to obtain a co-refining product.
[0065] Comparative Example 2
[0066] The co-refining product is obtained by directly mixing Xinjiang lignite with low-quality FCC oil slurry in a mass ratio of 1:3 and then performing co-refining hydrogenation reaction.
[0067] Comparative Example 3
[0068] The vitrinite high-enrichment coal sample obtained in Example 1 was mixed with low-quality DCC oil slurry in a mass ratio of 1:3 and then subjected to co-refining and hydrogenation reaction to obtain a co-refining product.
[0069] Comparative Example 4
[0070] The co-refining product is obtained by directly mixing Xinjiang lignite with low-quality DCC oil slurry in a mass ratio of 1:3 and then performing co-refining and hydrogenation reaction.
[0071] The results of the co-refining hydrogenation reactions of Comparative Examples 1 to 4 are shown in Table 6.
[0072] Table 6 Results of the co-refining hydrogenation reaction of Comparative Examples 1 to 4
[0073]
[0074]
[0075] It can be seen from Tables 3, 5 and 6 that the heavy components of the catalytic defocusing oil of the high-enriched coal sample of the inert group have a good co-refining effect after being mixed with low-quality FCC oil slurry / low-quality DCC oil slurry as co-refining oil. After low-quality FCC oil slurry / low-quality DCC oil slurry is mixed with the heavy components of the catalytic defocusing oil, it can meet the requirements of kerosene co-refining for co-refining oil. The above data also show that the effect of fractional utilization of the selected Xinjiang lignite is obvious, and the requirements of kerosene co-refining for raw coal can be met.
[0076] The various embodiments in this specification are described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the various embodiments can be referenced to each other.
[0077] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.
Claims
1. A kerosene co-refining method, characterized in that: The following steps are involved: S1. Separate the maceral enrichment from the raw coal in large quantities to obtain vitrinite-rich coal samples and inertinite-rich coal samples; S2. The inert group highly enriched coal sample is subjected to catalytic depolymerization treatment, and the product of the catalytic depolymerization treatment is divided into two parts, one part is subjected to distillation treatment to obtain heavy components; and the other part is subjected to semi-coke gasification treatment; S3, mixing the heavy component and the heavy oil to obtain co-refined oil, and mixing the co-refined oil with the vitrinite high-enriched coal sample to perform co-refining hydrogenation reaction to obtain a co-refining product; The mass ratio of the co-refined oil to the vitrinite high-enriched coal sample is 3:1; In step S2, the heavy component is heavy oil with a boiling point ≥ 400°C; In step S3, the heavy oil is one or more of low-quality FCC slurry oil and low-quality DCC slurry oil; In step S2, the specific steps of the catalytic depolymerization treatment are: spraying the catalyst solution on the inertinite group highly enriched coal sample for catalytic depolymerization treatment; The catalytic depolymerization treatment is carried out at a temperature of 650° C. and a time of 0.5 h; In terms of weight percentage, the composition of the catalyst solution is 10% ferric chloride, 5% methanol, 1.2% sodium dodecylbenzene sulfonate, and the balance is water; In step S3, the mass ratio of the heavy component to the heavy oil is 1:2; In step S3, the temperature of the co-refining hydrogenation reaction is 450° C., the time of the co-refining hydrogenation reaction is 1 hour, and the pressure of the co-refining hydrogenation reaction is 20 MPa.
2. The kerosene co-refining method according to claim 1, characterized in that: In the step S1, the raw coal is low-grade coal that is not conventionally used.
3. The kerosene co-refining method according to claim 2, characterized in that: The mass ratio of the catalyst solution to the inertinent highly enriched coal sample is 2-10:
100.
4. The kerosene co-refining method according to claim 1, characterized in that: In the step S3, the hydrogen for the co-refining hydrogenation reaction comes from the raw coal gas obtained by the catalytic depolymerization treatment in step S2 and the synthesis gas obtained by the semi-coke gasification treatment.