CN112342054B

CN112342054B - Processing method for co-producing process waste liquid and heavy raw oil by co-oxidation of propylene oxide

Info

Publication number: CN112342054B
Application number: CN201910720923.7A
Authority: CN
Inventors: 陈学峰; 魏晓丽; 龚剑洪; 张久顺
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2019-08-06
Filing date: 2019-08-06
Publication date: 2022-05-17
Anticipated expiration: 2039-08-06
Also published as: CN112342054A

Abstract

The invention relates to the field of catalytic cracking, and discloses a processing method for co-producing process waste liquid and heavy raw oil by a co-oxidation method of propylene oxide, wherein the processing method comprises the following steps: the co-production process waste liquid of the heavy raw oil and the propylene oxide is sequentially contacted with a catalytic cracking catalyst for catalytic cracking reaction to obtain a reaction product and a spent catalyst; separating the reaction product from the spent catalyst, regenerating the spent catalyst, and using the regenerated catalyst as the catalytic cracking catalyst. By adopting the processing method of the invention to process the co-production process waste liquid of the propylene oxide co-oxidation method and the heavy raw oil, the co-production process waste liquid of the propylene oxide co-oxidation method which is basically worthless can be converted into high-value products through a mature process, and meanwhile, compared with the comparative example, the yield of liquefied gas is improved by at least 14.5%, and the yield of gasoline is improved by at least 3%.

Description

Method for co-producing process waste liquid and heavy raw oil by co-oxidation of propylene oxide

Technical Field

The invention relates to a processing method for co-producing process waste liquid and heavy raw oil by a co-oxidation method of propylene oxide.

Background

Propylene Oxide (PO), also called Propylene Oxide and methyl ethylene Oxide, is the third largest Propylene derivative, second only to polypropylene and acrylonitrile, and is an important basic organic chemical synthesis raw material. Currently, industrially available methods for producing propylene oxide include chlorohydrin process, co-oxidation process, direct oxidation of hydrogen peroxide process, and cumene oxidation process. The chlorohydrin method is widely applied, has the advantages of good product selectivity, low purity required for raw material propylene, large operation load elasticity, short production process flow and low capital construction cost, but has the defects of low product quality, large water resource consumption in the production process, and generation of a large amount of wastewater and waste residues, and 40-50 tons of high-salinity wastewater and 1-1.5 tons of waste residues can be discharged when 1 ton of propylene oxide is produced. The co-oxidation method has great advantages in solving the pollution, corrosion and environmental protection of three wastes, can greatly improve the production scale of a single set of equipment, simultaneously can share part of the cost for co-production products (styrene, tert-butyl alcohol, methyl tert-butyl ether or cumene peroxide), and has stronger market competitive advantage.

The production process of propylene oxide coproduced with methyl tert-butyl ether (PO/MTBE) also has the problem of discharge of high-concentration waste liquid, and main organic pollutants in the discharged waste liquid are mostly formic acid, esters, alcohols, aldehydes, acetone, butanone, hydrocarbons and the like, and in addition, part of pollutants such as propylene oxide, pyrazoles, furans, pyrans and the like are also contained. The byproducts are generally used as heating furnace fuel for public works, but water in the waste liquid is easy to cause heating furnace fluctuation and has low fuel economy, and if ketones, alcohols or ethers in organic pollutants in the waste liquid can be further processed and utilized, the overall benefit of the process can be improved.

The process for preparing olefin by alcohol dehydration also has the problem of large discharge of high-concentration wastewater, and the current method for solving the problem of high-concentration wastewater discharge mainly adopts the means of extraction, steam stripping and the like, and adopts the mode of firstly converting high-concentration wastewater into low-concentration wastewater and then carrying out biochemical treatment. However, the conventional treatment method has problems of complicated flow process and high cost. The high concentration waste water in the process of preparing ethylene by cracking ethanol contains ethanol, ether, ethylene, C3 and hydrocarbon organic waste water. For example, CN105036437A discloses a treatment process of high-concentration wastewater from ethylene production by ethanol dehydration. The process adopts the treatment flow of flocculation precipitation, filtration, separation and post-treatment, and recycles and reuses the components contained in the high-concentration wastewater. For another example, CN104230618A discloses a water resource recycling process for preparing ethylene by ethanol dehydration, the process comprises heat exchanging the material at the outlet of the reactor for preparing ethylene by ethanol with a heat exchanger to recover heat, separating with a first-stage separation tower, controlling the temperature at the top of the separation tower at 105 ℃ and 110 ℃ directly, separating high-concentration wastewater with high organic content, and treating the high-concentration wastewater with high organic content to make it reach the discharge standard; and (3) separating the gas-phase material at the outlet by using a second-stage separation tower, controlling the temperature at the top of the second-stage separation tower to be 90-95 ℃, then obtaining a gas-phase mixture of ethanol and olefin from the top of the separation tower, and obtaining a concentrated solution from the bottom of the separation tower. The wastewater from the dimethyl ether production by methanol cracking also contains high concentration organic compounds. For example, CN101376550 provides a method for treating wastewater from a process for preparing dimethyl ether by dehydrating methanol, which indicates that the method comprises the following three process units: a first process unit for separating the process wastewater into two streams of organic-rich and organic-poor water streams by an evaporation process; the second process unit is used for carrying out membrane separation on the water flow rich in the organic matters, recovering the organic matters in the concentrated solution and recycling the water phase; and the third process unit is used for carrying out biochemical treatment on the waste water poor in organic matters so as to enable the water quality to meet the requirement of recycling circulating water. The above-mentioned wastewater treatment method is applicable to the treatment of high-concentration wastewater containing PO/MTBE, but the treatment process is long, the cost is high, and it is difficult to reuse useful substances in wastewater.

CN103086874A discloses a method for utilizing tertiary butanol co-produced by a propylene and isobutane co-oxidation process propylene oxide production device. The method comprises the steps of vaporizing a tert-butyl alcohol solution containing acetone, which is a byproduct of the device, forming a mixed gas with air, diluent gas and the like in a certain proportion, preheating, and then carrying out first-stage oxidation, adjusting the composition and temperature of an oxidation product obtained by the first-stage oxidation, and then carrying out second-stage oxidation, wherein an oxidation product obtained by the second-stage oxidation is absorbed to obtain a crude methacrylic acid aqueous solution which can be used for refining. The tertiary butanol co-produced by the method is directly used for preparing methacrylic acid without refining and purification. CN106336061A discloses a treatment method of high-concentration wastewater from preparation of isobutene through pyrolysis of a PO byproduct TBA, which comprises the following steps: carrying out catalytic hydrogenolysis reaction on high-concentration wastewater containing organic matters to form wastewater containing alcohols and alkanes; carrying out flash evaporation treatment on the wastewater containing alcohols and alkanes, extracting a material flow containing small molecular alcohols from the top of a flash tower, and extracting a material flow containing large molecular alcohols and alkanes from the bottom of the tower; physically separating the material flow containing the macromolecular alcohol and the Wantong material flow through a coagulator to separate the material flow containing the macromolecular alcohol and the alkane, and obtaining the wastewater which can be directly biochemically treated. The method can reduce the COD of the wastewater to below 500ppm, and the wastewater reaches the standard of direct discharge after biochemical treatment. CN103936574A discloses a method for preparing high-purity methyl isobutyl ketone by using industrial by-product waste liquid acetone. The method comprises the steps of enabling an industrial byproduct acetone mixed solution which is not subjected to impurity separation and purification and hydrogen to pass through a fixed bed reactor filled with a heterogeneous catalyst together to react in one step to obtain a reaction product, and simultaneously converting impurities in the byproduct acetone mixed solution into substances easy to separate; the unreacted acetone is recycled by rectifying the reaction product, and the methyl isobutyl ketone product with high alcohol purity is obtained after the other components are rectified and separated.

The method for treating the high-concentration waste liquid in the production of the propylene oxide can realize the recycling of valuable components in the waste liquid, but is only limited to a certain component, the separation and subsequent product refining processes are long, a newly-built device and investment are required, the cost is high, and the method is not economical for improving the benefit of resource recycling.

Disclosure of Invention

The invention aims to provide a novel processing method for co-producing process waste liquid and heavy raw oil by a co-oxidation method of propylene oxide, which not only can realize the recycling of valuable components in the waste liquid and reduce the difficulty of waste liquid treatment, but also can improve the yield of cracked gas and gasoline.

The inventor of the invention finds that catalytic cracking is carried out by contacting the co-oxidation process waste liquid of heavy raw oil and propylene oxide with a catalytic cracking catalyst in sequence, namely, slightly modifying the device on the basis of utilizing the mature heavy raw oil catalytic cracking process device, and converting oxygen-containing compounds and hydrocarbons of C7-C12 in the co-oxidation process waste liquid of propylene oxide into gasoline component products with higher value through proper feeding sequence and reaction environment, and converting small molecular oxygen-containing compounds (such as oxygen-containing compounds of C3 and C4) into hydrocarbon components with higher carbon number under specific conditions, so that the partially converted hydrocarbon components are converted into gasoline component products without influencing the catalytic cracking of heavy raw oil. On the premise of not increasing the treatment difficulty of the co-oxidation co-production process waste liquid of propylene oxide, the co-oxidation co-production process waste liquid of low-value propylene oxide is converted into a high-value product, and the economic benefit of the co-oxidation co-production process device of propylene oxide is obviously improved.

According to a preferred embodiment of the invention, the catalytic cracking is carried out on the co-oxidation process waste liquid of heavy raw oil and propylene oxide successively by adopting the riser reactor, the device is slightly changed on the basis of utilizing the riser reactor for the catalytic cracking of heavy raw oil, and the effective treatment on the co-oxidation process waste liquid of propylene oxide is realized by setting a proper feed inlet position and adjusting the reaction environment, so that the co-oxidation process waste liquid of propylene oxide can be further converted into a gasoline fraction product, the yield of gasoline components is improved, and part of liquefied gas can be increased.

In order to achieve the above object, the present invention provides a processing method for co-producing process waste liquid and heavy raw oil by co-oxidation of propylene oxide, the processing method comprising: sequentially contacting the co-oxidation process waste liquid of the heavy raw oil and the propylene oxide with a catalytic cracking catalyst for catalytic cracking reaction to obtain a reaction product and a spent catalyst; separating the reaction product from the spent catalyst, regenerating the spent catalyst, and using the regenerated catalyst as the catalytic cracking catalyst.

Preferably, the co-oxidation process waste liquid of the heavy raw oil and the propylene oxide is fed into the riser reactor to contact with a catalytic cracking catalyst for catalytic cracking reaction, and the feeding port of the co-oxidation process waste liquid of the propylene oxide is arranged at the downstream of the feeding port of the heavy raw oil according to the flow direction of reaction materials in the riser reactor.

Preferably, according to the flow direction of the reaction materials in the riser reactor, the distance between the feed inlet of the heavy raw oil and the feed inlet of the waste liquid of the co-oxidation process co-production process of propylene oxide accounts for 2-20%, more preferably 3-15%, and even more preferably 3-10% of the height of the riser reactor;

the catalytic cracking catalyst feeding port is positioned at the lower part of the feeding port of the waste liquid of the co-production process of the propylene oxide co-oxidation method, and is more preferably positioned at the bottom of the riser reactor.

By adopting the processing method, the co-oxidation process co-production process waste liquid of the low-value propylene oxide is converted into the high-value product, the resource recycling is realized, the economic benefit of the co-oxidation process co-production process device of the propylene oxide is obviously improved, the yield of gasoline components can be improved on the premise of not increasing the treatment difficulty of the co-oxidation process co-production process waste liquid of the propylene oxide, and part of liquefied gas is increased, and the yield of the liquefied gas is improved by at least 14.5%, and can be improved by 28% better; the gasoline yield is improved by at least 3 percent, and more preferably, the gasoline yield can be improved by 9.4 percent.

Moreover, the processing method solves the problems of reasonable and efficient utilization of the co-oxidation process waste liquid of the propylene oxide, particularly the PO/MTBE waste liquid, on the one hand, and the shortage of petrochemical raw materials on the other hand, and improves the economic benefit and the social benefit of the petrochemical industry.

In addition, the processing method is suitable for other process units which adopt a co-oxidation method to prepare PO co-product products, including PO/MTBE process units, and can be realized by slightly adjusting mature catalytic cracking process units, so that the investment cost is effectively controlled.

Drawings

Fig. 1 is a schematic flow chart of a processing method according to an embodiment of the present invention, and also includes a schematic structural diagram of an embodiment of the system according to the present invention.

Description of the reference numerals

I-a first reaction zone; II-a second reaction zone;

1-a riser reactor; 2-a regenerator; 3-a settler; 4-a stripping section;

5- (outlet end of riser reactor 1) first cyclone;

6- (outlet end of riser reactor 1) second cyclone;

7- (a gas outlet of the first cyclone separator 5 and the second cyclone separator 6 is communicated with a large oil gas pipeline 19) is used for collecting gas;

8-a first to-be-regenerated catalyst inclined pipeline;

9-a first to-be-regenerated slide valve;

10-a second spent catalyst inclined pipeline;

11- (connecting the regenerator 2 with the riser reactor 1) a third regenerated catalyst inclined pipeline;

12- (connecting the regenerator 2 with the riser reactor 1) a fourth regenerated catalyst inclined pipeline;

13-a second regenerative spool valve;

14- (for the riser reactor 1 to convey pre-lift medium) pre-lift medium line;

15- (for riser reactor 1 feed) heavy feed oil line;

16- (for riser reactor 1 to deliver mist steam) mist steam line;

a feeding pipeline for co-producing process waste liquid by a co-oxidation method of 17-propylene oxide;

18-stripping steam line;

19-large oil gas line;

20- (regenerator 2) main wind inlet line;

21-an air distributor;

22-regenerator cyclone;

23- (communicating with the gas outlet of the cyclone 22) flue gas duct.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

According to the invention, the processing method for co-producing the process waste liquid and the heavy raw oil by the co-oxidation method of the propylene oxide comprises the following steps: sequentially contacting the co-oxidation process waste liquid of the heavy raw oil and the propylene oxide with a catalytic cracking catalyst for catalytic cracking reaction to obtain a reaction product and a spent catalyst; separating the reaction product from the spent catalyst, regenerating the spent catalyst, and using the regenerated catalyst as the catalytic cracking catalyst.

According to the invention, the co-oxidation process co-production process waste liquid of the propylene oxide is later than the contact of the heavy raw oil and the catalytic cracking catalyst, so that the oxygen-containing compounds and hydrocarbons of C7-C12 in the waste liquid can be converted into gasoline component products with higher value under mild catalytic cracking conditions, and meanwhile, small molecular oxygen-containing compounds (such as oxygen-containing compounds of C3 and C4) are converted into hydrocarbon components with higher carbon number under specific conditions, so that the partially converted hydrocarbon components are converted into the gasoline component products without influencing the catalytic cracking of the heavy raw oil.

According to the present invention, the catalytic cracking reaction of the co-oxidation process waste liquid of propylene oxide after the contact of the heavy feedstock oil with the catalytic cracking catalyst can be carried out in various reaction apparatuses known in the art to be capable of carrying out catalytic cracking. In view of ensuring the full reaction of the co-production process waste liquid of the propylene oxide co-oxidation method, the co-production process waste liquid of the heavy raw oil and the propylene oxide is sent into the riser reactor to contact with a catalytic cracking catalyst for catalytic cracking reaction, and a feed inlet of the co-production process waste liquid of the propylene oxide is arranged at the lower part of the feed inlet of the heavy raw oil according to the flow direction of reaction materials in the riser reactor.

According to the present invention, such riser reactors are well known to those skilled in the art. For example, the riser reactor may be a constant diameter riser reactor or a variable diameter riser reactor, and specifically, the variable diameter riser reactor may be, for example, a constant linear velocity riser reactor.

The riser reactor can be provided with a plurality of feed inlets, the feeding proportion of each feed inlet can be the same or different, and different feed inlets and feeding positions can be arranged according to different feeding. Specifically, the number of the feed openings may be two or more, and according to a preferred embodiment of the present invention, the feed openings include: a heavy raw oil feed port and a propylene oxide co-oxidation process co-production process waste liquid feed port.

The riser reactor can comprise a pre-lifting section and at least one reaction zone from bottom to top, and the number of the reaction zones can be 2-8, preferably 2-3, in order to enable the raw materials to be fully reacted and meet different target product quality requirements. Preferably, the co-oxidation process waste liquid of the heavy raw oil and the propylene oxide is introduced into the riser reactor from different feed inlets of the riser reactor. Further preferably, the feed inlet of the co-oxidation process waste liquid of propylene oxide is arranged at the downstream of the feed inlet of the heavy raw oil according to the flow direction of the reaction materials in the riser reactor. That is, the flow direction of the reaction materials in the riser reactor flows from bottom to top, so that the feeding port of the waste liquid in the co-oxidation process of propylene oxide co-production is arranged above the feeding port of the heavy raw oil. Further preferably, in order to sufficiently catalytically crack the C7-C12 oxygen-containing compound and hydrocarbons in the co-oxidation process waste liquid of propylene oxide to convert into gasoline component products and simultaneously convert the small molecular oxygen-containing compound (such as oxygen-containing compounds of C3 and C4) into higher carbon number hydrocarbon components under specific conditions, so that the partially converted hydrocarbon components are converted into gasoline component products, the distance between the feed inlet of the heavy raw oil and the feed inlet of the co-oxidation process waste liquid of propylene oxide accounts for 2-20%, more preferably 3-15%, and still more preferably 3-10% of the height of the riser reactor according to the flow direction of the reaction materials in the riser reactor.

According to the present invention, preferably, in order to allow the co-production process waste liquid of the heavy raw oil and propylene oxide to contact the catalytic cracking catalyst in sequence for catalytic cracking reaction, the catalytic cracking catalyst feed inlet is located at the lower part of the heavy raw oil feed inlet, and more preferably, at the bottom of the riser reactor.

According to the present invention, the co-production process waste liquid of propylene oxide includes waste liquid in various processes for preparing Propylene Oxide (PO) and co-producing products by using a co-oxidation method, for example, the co-production process waste liquid of propylene oxide may be at least one selected from co-production process waste liquid of methyl tert-butyl ether by using a co-oxidation method of propylene oxide, co-production process waste liquid of styrene by using propylene oxide, co-production process waste liquid of tert-butyl alcohol by using a co-oxidation method of propylene oxide, and co-production process waste liquid of cumene peroxide by using a co-oxidation method of propylene oxide. However, the inventor of the invention finds that the processing method is more suitable for the conversion of the co-production of methyl tert-butyl ether process waste liquid (PO/MTBE) by the co-oxidation method of propylene oxide, and thus the processing effect of the processing method is embodied. Wherein the PO/MTBE waste stream contains, but is not limited to: based on the total weight of the PO/MTBE waste liquid, the PO/MTBE waste liquid contains 10-30 wt% of water, 10-30 wt% of hydrocarbons and 40-80 wt% of oxygen-containing compounds; based on the total weight of the oxygen-containing compounds, the oxygen-containing compounds comprise 10-85% of ketone compounds, 0-50% of alcohol compounds, 0-30% of ether compounds and 0-10% of aldehydes and ester compounds.

The types of heavy feedstocks are well known to those skilled in the art in accordance with the present invention. For example, the heavy feedstock may be heavy hydrocarbons and/or various animal and vegetable oil-type feedstocks rich in hydrocarbons. The heavy hydrocarbon may be a mixture of one or more selected from the group consisting of petroleum hydrocarbons, mineral oils and synthetic oils. The petroleum hydrocarbon can be one or more of vacuum wax oil, atmospheric residue, vacuum wax oil blending part vacuum residue and other hydrocarbon oil obtained by secondary processing. The hydrocarbon oil obtained by the secondary processing may be, for example, one or more of coker gas oil, deasphalted oil, and furfural refined raffinate oil. The mineral oil may be a mixture of one or more selected from coal liquefaction oil, oil sand oil and shale oil. The synthetic oil can be distillate oil obtained by F-T synthesis of coal, natural gas or asphalt. The various animal and vegetable oils rich in hydrocarbon can be various animal and vegetable oils. Preferably, the heavy feedstock is selected from one or more of vacuum wax oil, atmospheric resid, vacuum resid, coker wax oil, coker resid, and fischer-tropsch wax oil.

According to the present invention, the conditions of the catalytic cracking reaction generally include reaction temperature and reaction time. Under the feeding sequence that the co-oxidation process waste liquid of the heavy raw oil and the propylene oxide is sequentially contacted with a catalytic cracking catalyst, in order to further ensure the full reaction of the heavy raw oil and the propylene oxide, further improve the yield of gasoline distinguishing products and increase the yield of liquefied gas, the catalytic cracking reaction conditions comprise: the reaction temperature (outlet temperature, the same below) is 450-650 ℃, the reaction time is 0.1-10 seconds, and the reaction pressure (gauge pressure, the same below) is 0.05-1 MPa. Preferably, the reaction temperature is 480-600 ℃ and the reaction time is 0.5-6 seconds. More preferably, the reaction temperature is 500-580 ℃ and the reaction time is 1-4 seconds. The weight ratio of the catalytic cracking catalyst to the heavy raw oil can be 1-100, and preferably, the weight ratio of the catalytic cracking catalyst to the heavy raw oil is 3-40; more preferably, the weight ratio of the catalytic cracking catalyst to the heavy feed oil is 5 to 30.

According to a preferred embodiment of the present invention, the processing method further comprises: the co-oxidation method co-production process waste liquid of the propylene oxide is preheated to 350-450 ℃, more preferably 380-420 ℃ before the co-production process waste liquid of the propylene oxide is contacted with the catalytic cracking catalyst, and then is sent into the riser reactor to be contacted with the catalytic cracking catalyst.

According to the invention, the conditions of the catalytic cracking reaction further comprise: the feeding weight ratio of the co-oxidation process waste liquid of the propylene oxide to the heavy raw oil per unit time is preferably (0.05-0.3):1, and the weight ratio of the atomized water vapor to the heavy raw oil can be (0.01-1): 1.

The catalytic cracking catalyst provided by the invention can be used for catalytically cracking the co-production process waste liquid and heavy raw oil by the epoxypropane co-oxidation method. The catalytic cracking catalyst is commercially available or may be prepared according to methods known to those skilled in the art. In particular, the catalytic cracking catalyst contains a zeolite, an inorganic oxide, and optionally a clay. According to the invention, the catalytic cracking catalyst contains, on a dry basis and based on the total weight of the catalytic cracking catalyst, from 1 to 60% by weight of zeolite, from 5 to 99% by weight of inorganic oxide and from 0 to 70% by weight of clay. Preferably, to increase the yield of propylene and butenes, on a dry basis and based on the total weight of the zeoliteSaid zeolite comprising from 50 to 100 weight percent of a medium pore zeolite and from 0 to 50 weight percent of a large pore zeolite; more preferably, the zeolite contains 70 to 95 wt% of the medium pore zeolite and 5 to 30 wt% of the large pore zeolite, on a dry basis and based on the total weight of the zeolite. The medium and large pore zeolites are defined as conventional in the art, i.e., the medium pore zeolite has an average pore size of 0.5 to 0.6nm and the large pore zeolite has an average pore size of 0.7 to 1 nm. The medium pore zeolite may be a zeolite having an MFI structure, such as a ZSM-series zeolite and/or a ZRP zeolite, which may also be modified with a nonmetallic element such as phosphorus and/or a transition metal element such as iron, cobalt, nickel, as described in more detail in U.S. Pat. No. 5,232,675, and the ZSM-series zeolite is selected from one or more mixtures of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other zeolites of similar structure, as described in more detail in US3,702,886. The large pore zeolite may be selected from one or more of rare earth Y (rey), rare earth hydrogen Y (rehy), ultrastable Y and high silicon Y. The inorganic oxide may be silicon dioxide (SiO) as a binder₂) And/or aluminum oxide (Al)₂O₃). The clay as a matrix (carrier) may be kaolin and/or halloysite.

According to the invention, a reaction product and a spent catalyst are obtained after the catalytic cracking reaction, the reaction product and the spent catalyst are separated, the obtained spent catalyst is regenerated, and the regenerated catalyst is used as the catalytic cracking catalyst. The obtained reaction product is separated into fractions such as dry gas, liquefied gas, cracked gasoline, cracked diesel oil and the like through a subsequent separation system, and the invention is not described in detail herein.

The process for regenerating the spent catalyst according to the invention is well known to the person skilled in the art. Preferably, the obtained spent catalyst is contacted with oxygen-containing gas in a regenerator for coke-burning regeneration. In the regeneration process, an oxygen-containing gas is generally introduced from the bottom of the regenerator, after the oxygen-containing gas, such as air or oxygen, is introduced into the regenerator, the spent catalyst is contacted with the oxygen-containing gas for burning and regeneration, the flue gas generated after the spent catalyst is burned and regenerated is subjected to gas-solid separation at the upper part of the regenerator, and the flue gas enters a subsequent energy recovery system. According to the invention, when the heavy raw material and the co-production process waste liquid of the propylene oxide co-oxidation method are sequentially contacted with the catalytic cracking catalyst in the riser reactor to carry out catalytic cracking reaction, preferably, the regenerated catalyst is returned to the riser reactor to be used as the catalytic cracking catalyst. The conditions for regeneration are well known to those skilled in the art and may include, in particular: the regeneration temperature is 550-750 ℃, preferably 600-730 ℃, and more preferably 650-700 ℃; the apparent linear velocity of the oxygen-containing gas is 0.5 to 3 m/s, preferably 0.8 to 2.5 m/s, more preferably 1 to 2 m/s; the average residence time of the spent catalyst is from 0.6 to 3 minutes, preferably from 0.8 to 2.5 minutes, more preferably from 1 to 2 minutes.

According to the invention, the processing method further comprises: before returning the regenerated catalyst to the riser reactor for use as the catalytic cracking catalyst, the regenerated catalyst from the regenerator is fed to a degassing tank for degassing and then fed to the riser reactor for use as the catalytic cracking catalyst, an oxygen-containing gas obtained by degassing in the degassing tank is returned to the regenerator, and the regenerated catalyst in the degassing tank is subjected to removal of impurities such as the oxygen-containing gas by a stripping gas such as steam.

The invention will be further illustrated by means of a specific embodiment in conjunction with fig. 1, but the invention is not limited thereto.

As shown in fig. 1, the process flow of the processing method provided by the present invention includes: the pre-lifting medium enters from the bottom of the riser reactor 1 through a pre-lifting medium pipeline 14, the regenerated catalyst from a fourth regenerated catalyst inclined pipeline 12 enters the bottom of the riser reactor 1 after being regulated by a second regeneration slide valve 13, moves upwards and accelerates along the riser reactor under the lifting action of the pre-lifting medium, and is firstly atomized with preheated heavy raw oil from a heavy raw oil pipeline 15 through atomizing steam of an atomizing steam pipeline 16 and brought into the riser reactor to contact with the catalyst in a first reaction zone I for reaction. The oil mixture continues to move upwards and contacts and reacts with PO/MTBE waste liquid introduced by a co-oxidation process waste liquid feeding pipeline 17 of propylene oxide in the second reaction zone II. And then the generated reaction product oil gas and the inactivated spent catalyst enter a second cyclone separator 6 in the settler 3 to realize the separation of the spent catalyst and the reaction product oil gas, the reaction product oil gas enters a gas collection chamber 7, and catalyst fine powder returns to the settler 3 through a dipleg. Spent catalyst in settler 3 flows to stripping section 4 and contacts steam from stripping steam line 18. The reaction product oil gas extracted from the spent catalyst enters a gas collection chamber 7 after passing through a cyclone separator. The stripped spent catalyst enters the regenerator 2 after being regulated by a first spent slide valve 9, air from a main air inlet pipeline 20 enters the regenerator 2 after being distributed by an air distributor 21, coke on the spent catalyst in a dense bed layer at the bottom of the regenerator 2 is burned off to regenerate the inactivated spent catalyst, and flue gas enters a subsequent energy recovery system through an upper gas flue gas pipeline 23 of a cyclone separator 22 of the regenerator. Wherein the pre-lifting medium can be dry gas, water vapor or a mixture thereof. The regenerated catalyst circulates to the bottom of the riser reactor 1 through a fourth regenerated catalyst inclined pipeline 12, the catalyst circulation amount can be controlled through a second regenerated slide valve 13, gas returns to the regenerator 2 through a third regenerated catalyst inclined pipeline 11, and reaction product oil gas in the gas collection chamber 7 enters a subsequent separation system through a large oil gas pipeline 19.

The present invention will be described in detail below by way of examples.

In the following examples and comparative examples, the co-oxidation co-production process waste liquid of propylene oxide is PO/MTBE waste liquid, and the heavy raw oil is daqing atmospheric residue, and the properties thereof are shown in tables 1 and 2, respectively.

The catalytic cracking catalyst used in the following examples and comparative examples was sold under the trade designation MLC-500, produced by the catalyst division of Qilu catalyst works, China petrochemical Co., Ltd., and the properties are shown in Table 3.

In the following examples and comparative examples, the COD content in the wastewater was determined by the potassium dichromate method (GB/T11914-.

Comparative example 1

The tests were carried out on a pilot plant of a riser reactor. The raw oil is heavy raw oil, the preheated heavy raw oil (preheated to 230 ℃) enters the bottom of a riser reactor to carry out catalytic cracking reaction, a reaction product and a spent catalyst enter a closed cyclone separator from the outlet of the reactor, the reaction product and the spent catalyst are quickly separated, and the reaction product is cut according to the distillation range in a separation system, so that fractions such as propylene, butylene, pyrolysis gasoline and the like are obtained.

The spent catalyst enters a stripping section under the action of gravity, hydrocarbon products adsorbed on the spent catalyst are stripped by steam, and the stripped spent catalyst enters a regenerator and is in contact with air for regeneration; the regenerated catalyst enters a degassing tank to remove oxygen-containing gas adsorbed and carried by the regenerated catalyst; the degassed regenerated catalyst returns to the riser reactor for recycling; the operating conditions and the product distribution are listed in Table 4.

Example 1

The experiment was carried out according to the scheme of FIG. 1. The raw materials comprise: PO/MTBE waste liquid and heavy raw oil. The catalytic cracking reaction is carried out on a medium-sized device of the reducing riser reactor. The preheated heavy raw oil (preheated to 230 ℃) enters the lower part of the riser reactor, and the PO/MTBE waste liquid enters the riser reactor from the diameter-expanding reaction zone to carry out catalytic cracking reaction. The pre-lifting medium enters from the bottom of the riser reactor through a pre-lifting medium pipeline, the regenerated catalyst from a fourth regenerated catalyst inclined pipe pipeline enters from the bottom of the riser reactor after being regulated by a second regeneration slide valve, and moves upwards in an accelerated manner along the riser reactor under the lifting action of the pre-lifting medium, the pre-lifting medium and the preheated heavy raw oil from the heavy raw oil feeding pipeline are atomized by the atomizing steam of the atomizing steam pipeline and are brought into the riser reactor to contact with the catalyst to react (a first reaction zone I), and then the pre-lifting medium moves upwards continuously to contact and react with PO/MTBE waste liquid of a waste liquid feeding pipeline of a co-oxidation process co-production process of propylene oxide (a second reaction zone II). The distance between the heavy raw oil feed inlet and the PO/MTBE waste liquid feed inlet accounts for 5% of the height of the riser reactor, and the feeding weight ratio of the PO/MTBE waste liquid to the heavy raw oil per unit time is 0.1: 1.

And the reaction product and the spent catalyst enter a closed cyclone separator from the outlet of the reactor, the reaction product and the spent catalyst are quickly separated, and the reaction product is cut in a separation system according to the distillation range, so that fractions such as dry gas, liquefied gas, gasoline, diesel oil and the like are obtained. The spent catalyst enters a stripping section under the action of gravity, hydrocarbon products adsorbed on the spent catalyst are stripped by steam, the stripped catalyst enters a regenerator and is in contact with air for regeneration, the regeneration temperature is 700 ℃, the apparent linear speed of the air is 1.2 m/s, and the average residence time of the spent catalyst is 1.5 minutes. The regenerated catalyst enters a degassing tank to remove oxygen-containing gas adsorbed and carried by the regenerated catalyst, and the degassed regenerated catalyst returns to the riser reactor for recycling. The operating conditions and the product distribution are listed in Table 4.

Example 2

Heavy feed oil and PO/MTBE waste liquid were fed into the riser reactor to contact the catalytic cracking catalyst in sequence according to the method of example 1, except that the distance between the heavy feed oil feed port and the PO/MTBE feed port was 5% of the height of the riser reactor according to the flow direction of the reaction material in the riser reactor. The operating conditions and the product distribution are listed in Table 4.

Example 3

Heavy feed oil and PO/MTBE waste liquid were fed into the riser reactor to contact with the catalytic cracking catalyst successively in the same manner as in example 1, except that the feed weight ratio per unit time of PO/MTBE waste liquid to heavy feed oil was 0.2: 1. The operating conditions and the product distribution are listed in Table 4.

Example 4

Heavy feed oil and PO/MTBE waste liquid were fed into the riser reactor to contact with the catalytic cracking catalyst in sequence according to the method of example 1, except that the operating conditions were changed, and the specific operating conditions and product distribution were as shown in table 4.

TABLE 1

Composition of raw materials	Weight (D)％
		Water (I)	7.49
Methanol	0.68
		Acetone (II)	41.22
Acetic acid	3.93
		Ethylene glycol	5.04
Tert-butyl alcohol	13.44
		Isobutyric acid (Ab)	2.17
1-tert-butyl-2-propanol	9.45
		Formic acid butyl ester	0.23
Ethylene glycol Ether	1.68
		Hydrocarbons	14.67

TABLE 2

TABLE 3

TABLE 4

The water-oil weight ratio refers to the ratio of the weight of atomized water vapor to the weight of heavy raw oil; the catalyst oil weight ratio refers to the ratio of the weight of the catalyst to the weight of the heavy feed oil.

As can be seen from the results of table 4, the yields of liquefied gas and gasoline in comparative example 1 were 15.98 wt% and 45.68 wt%, respectively. The yields of liquefied gas and gasoline were 18.31 wt% and 49.57 wt%, respectively, in example 1, 18.86 wt% and 48.99 wt% respectively, in example 2, 18.56 wt% and 49.97 wt% respectively, in example 3, and 20.56 wt% and 47.08 wt% respectively, in example 4. In addition, the COD content in the wastewater is increased by less than 150mg/L, and the increase of the COD content in the wastewater is not obvious. Therefore, the method for co-producing the process waste liquid by the co-oxidation method for treating the propylene oxide through catalytic cracking does not increase the treatment difficulty of the waste liquid, and simultaneously, the yield of the liquefied gas is improved by at least 14.5 percent, and more preferably by 28 percent; the gasoline yield is improved by at least 3 percent, and more preferably, the gasoline yield can be improved by 9.4 percent.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the content of the present invention as long as it does not depart from the gist of the present invention.

Claims

1. A processing method for co-producing process waste liquid and heavy raw oil by a co-oxidation method of propylene oxide is characterized by comprising the following steps:

the co-oxidation process co-production process waste liquid of heavy raw oil and propylene oxide is contacted with a catalytic cracking catalyst in sequence according to the flow direction of reaction materials in a riser reactor to carry out catalytic cracking reaction, so as to obtain a reaction product and a spent catalyst; the conditions of the catalytic cracking reaction include: the reaction temperature is 450-650 ℃, the reaction time is 0.1-10 seconds, the weight ratio of the catalytic cracking catalyst to the heavy raw oil is 1-100, the weight ratio of the co-oxidation process co-production process waste liquid of the propylene oxide to the heavy raw oil is (0.05-0.3) to 1, and the weight ratio of the atomized water vapor to the heavy raw oil is (0.01-1) to 1; according to the flow direction of reaction materials in the riser reactor, the distance between a heavy raw oil feed inlet and a propylene oxide co-oxidation process co-production process waste liquid feed inlet accounts for 2-20% of the height of the riser reactor;

separating the reaction product from the spent catalyst, regenerating the spent catalyst, and using the regenerated catalyst as the catalytic cracking catalyst.

2. The processing method according to claim 1, wherein the co-oxidation process waste liquid of propylene oxide is at least one selected from co-oxidation process waste liquid of propylene oxide with co-production of methyl tert-butyl ether, co-oxidation process waste liquid of propylene oxide with co-production of styrene, co-oxidation process waste liquid of propylene oxide with co-production of tert-butyl alcohol, and co-oxidation process waste liquid of propylene oxide with co-production of cumene peroxide;

the heavy raw oil is selected from one or more of vacuum wax oil, atmospheric residue oil, vacuum residue oil, coker wax oil, coker residue oil and Fischer-Tropsch wax oil.

3. The process as claimed in claim 1, wherein the reaction temperature is 480-.

4. The process as claimed in claim 3, wherein the reaction temperature is 500-580 ℃, the reaction time is 1-4 s, and the weight ratio of the catalytic cracking catalyst to the heavy raw oil is 5-30.

5. The process of claim 1, 3 or 4 wherein the catalytic cracking catalyst comprises a zeolite, an inorganic oxide and optionally a clay;

on a dry basis and based on the total weight of the catalytic cracking catalyst, the catalytic cracking catalyst comprises 1-60 wt% zeolite, 5-99 wt% inorganic oxide, and 0-70 wt% clay;

the zeolite contains 50 to 100 wt% of a medium pore zeolite and 0 to 50 wt% of a large pore zeolite, on a dry basis and based on the total weight of the zeolite.

6. The process of claim 5 wherein the zeolite comprises from 70 to 95 weight percent of the medium pore zeolite and from 5 to 30 weight percent of the large pore zeolite, on a dry basis and based on the total weight of the zeolite.

7. The process of claim 5, wherein the medium pore zeolite is a ZSM-series zeolite and/or a ZRP zeolite, and the large pore zeolite is selected from one or more of rare earth Y, rare earth hydrogen Y, ultrastable Y, and high silicon Y;

the inorganic oxide is silicon dioxide and/or aluminum oxide;

the clay is kaolin and/or halloysite.

8. The process according to any one of claims 1 to 4, wherein the co-oxidation process waste liquid of propylene oxide and the heavy raw oil are fed into the riser reactor to contact with a catalytic cracking catalyst for catalytic cracking reaction, and the feed inlet of the co-oxidation process waste liquid of propylene oxide is located downstream of the feed inlet of the heavy raw oil according to the flow direction of the reaction materials in the riser reactor.

9. The processing method according to claim 8, wherein the distance between the feed inlet of the heavy raw oil and the feed inlet of the waste liquid of the co-oxidation process of propylene oxide coproduction process accounts for 3-15% of the height of the riser reactor according to the flow direction of the reaction materials in the riser reactor;

the feed inlet of the catalytic cracking catalyst is positioned at the lower part of the feed inlet of the waste liquid of the co-production process of the epoxypropane co-oxidation method.

10. The processing method according to claim 9, wherein the distance between the feed inlet of the heavy raw oil and the feed inlet of the co-oxidation process waste liquid of propylene oxide accounts for 3-10% of the height of the riser reactor;

the catalytic cracking catalyst feed inlet is located at the bottom of the riser reactor.

11. The processing method according to any one of claims 1 to 4, wherein the processing method further comprises: preheating the co-oxidation method co-production process waste liquid of the propylene oxide to 350-450 ℃ before the co-oxidation method co-production process waste liquid of the propylene oxide contacts the catalytic cracking catalyst.

12. The process as claimed in claim 11, wherein the co-oxidation process effluent of propylene oxide is preheated to 380-420 ℃ prior to contacting the co-oxidation process effluent of propylene oxide with the catalytic cracking catalyst.

13. The process according to claim 8, wherein the spent catalyst is subjected to coke-burning regeneration by contacting it with an oxygen-containing gas in a regenerator.

14. The machining method according to claim 13, wherein the machining method further comprises: and before returning the regenerated catalyst to the riser reactor to be used as the catalytic cracking catalyst, feeding the regenerated catalyst into a degassing tank for degassing, and returning oxygen-containing gas obtained after degassing to a regenerator.