Background of the Invention:

[0001] Refineries have numerous catalytic reactors including reformers, hydro-processors, isomerization units, and Claus units. Catalysts lose effectiveness and activity due to build-up of heavy hydrocarbon deposits and presence of process poisons. Many catalysts need to be changed after three or four years for example, where the reactor is de-inventoried of product and the spent catalyst is decontaminated, cooled, and safely un-loaded. Decontamination is usually required to avoid hazards in unloading, for example by removing light hydrocarbons that have a lower explosive limit (hereinafter, “LELs”), or hydrogen sulfide (EES) which has a lower explosive limit but that is also toxic. While oils or hydrocarbon deposits are less hazardous, they can clump catalyst particles together with pockets of the afore-mentioned LELs and coat catalyst surfaces, making full LEL removal harder. Most of the catalyst change-out steps are undertaken under an inert or substantially oxygen-free atmosphere to mitigate LEL explosion or if the catalyst material is pyrophoric or if pyrophoric contaminants are present.

[0002] After de-inventorying of product from the reactor, some refineries choose to cool the catalyst, flood it with water, and remove it as a slurry (hereinafter “wet dump”) to avoid the decontamination step, but this presents an even larger waste disposal issue. Most of the catalyst decontamination methods include techniques performed at elevated temperature (typically greater than 250 °F) since heat aids in removal of contaminants through stripping and vaporization. Many refineries will decontaminate the catalyst at temperatures ranging from about 350 to 400°F using vaporized cleaning solvents carried in hot process gas or steam (vapor phase cleaning as described in U.S. Patent Nos. 8,480,812 and 9,017,488 assigned to Refined Technologies, Inc.). This is particularly effective in solubilizing and removing oils and heavy hydrocarbon deposits. The carrier gas, or steam, is also used to effectively desorb LELs at a similar temperature. If the reactor is relatively choked with oil or heavy hydrocarbon deposits a preceding wash with diesel or similar may be performed. If the reactor is relatively free of oils or heavy hydrocarbon deposits, then the cleaning solvent may not be needed and the decontamination step can be simplified to just LEL-desorption using hot carrier gas or nitrogen (hereinafter “hot strip”). [0003] Injection of solvents into the reactor system is a relatively short process in the decontamination and cooling process. The introduction of solvent could be as short as a couple of hours whereas the cooldown portion of the reactor turn-around could take as long as 2-3 days. This is because there might be up to a million pounds of total catalyst and inert weight to cool. The subsequent cool-down step after decontamination is often accelerated by injecting cold nitrogen (N2) into the reactor, according to established offerings such as “Once-through cooling”, “NiCool®” or “JetCool™ , by the assignee of this invention, Linde. These assisted cooling techniques can save many hours to the customer and thus provide time saving value. Before any catalyst change-out work can be performed on these units, the reactors must be cooled to ensure process and personnel safety. Refineries commonly use recycle compressors to recirculate nitrogen or process gas through reactors early in the procedure with heat rejection to the atmosphere or cooling water via a heat exchanger. The high initial cooling rate cannot be sustained as the reactor cools below 300°F since the heat exchange temperature differential diminishes. This is when assisted cooldowns can sustain the rapid cooling rate using the capabilities of nitrogen pumping equipment to perform a Once-Through or NiCool or JetCool service. During a Once-Through cooldown, cool nitrogen gas (at temperatures as low as about 40°F) is flowed through the reactor and vented after one pass. In the NiCool method, liquid nitrogen is injected or sparged into a recirculated gas stream before the gas enters the reactor, to achieve a temperature as low as 40°F. This technique might consume about one-third the amount of nitrogen as a Once-Through cooldown. The JetCool method of cooldown utilizes a jet compressor, a type of pump that uses pressure energy of a motive fluid converted to velocity energy, to create a suction zone in the body of the jet compressor. The jet compressor is used to enable partial recirculation of the process stream effluent combined with fresh coolant gas. The temperature of the combined fluid is controlled by raising or lowering the temperature of the fresh coolant gas and manipulating the ratio of the recirculated effluent gas to fresh coolant gas, and again may be as low as about 40°F.

[0004] The decontamination and cooling steps are typically conducted at elevated pressures ranging from 50 to 300 psig or more to minimize pressure drop and allow higher mass flows through the system.

[0005] A new decontamination service marketed as IN2ERT™, accelerated purging and cleaning services, has been successfully developed by Linde for application in tanks, process vessels and heat exchangers for instance. Liquid phase solvents are misted into nitrogen gas and passed through contaminated equipment to effect vapor space and equipment surface decontamination. This is described in U.S. Patent Application Publication No. 2021/0340469 Al to Zachariah et al. and incorporated by reference in its entirety.

Summary of the Invention

[0006] 1. In one aspect of the invention, a method for decontaminating a reactor system containing at least one catalyst is provided. The method includes: a. providing a water-free carrier gas from a water-free carrier gas source at a first mass flow rate; b. providing a non-aqueous liquid solvent from a non-aqueous liquid solvent source at a second mass flow rate, and adding said solvent to said carrier gas to create a mist of liquid solvent droplets in carrier gas, wherein said non-aqueous liquid solvent and said carrier gas are provided at a mass flow rate ratio in the range 0.1 to 8; the delivered mist has a temperature in the range 50 to 400°F and a pressure in the range 50 to 500 psig, wherein a majority of the provided solvent remains a liquid phase in the delivered mist; c. delivering said mist into the reactor system and contacting the mist with at least a portion of the catalyst, wherein the initial temperature of said at least a first portion of catalyst in the reactor is between 250 and 450°F prior to delivering said solvent mist into the reactor system; and d. removing contaminants from the reactor system, wherein a substantial amount of said contaminants are solubilized by said solvent and removed from said reactor system in a vapor or liquid form.

[0007] Whilst a fine mist of liquid solvent droplets in carrier gas is preferred, it is more generally only required to disperse the liquid solvent in the carrier gas such that it can be effectively transported by the carrier gas to the reactor that is to be decontaminated. The term mist and liquid dispersion are used herein interchangeably. A high shear mixer is advantageously used to aid formation of the mist, wherein the high shear mixer comprises at least one of an eductor, a spray nozzle, an orifice, and a tee. As can be appreciated by those skilled in the art, other high shear mixing devices can also be utilized. [0008] The carrier gas is considered substantially water-free but may have minor amounts of water vapor at less than about 100 ppm on a volume basis. The solvent is considered nonaqueous but may have minor amounts of water present at less than about 1% on a weight basis.

Brief Description of the Figures

[0009] The above and other aspects, features, and advantages of the present invention will be more apparent from the following figures, wherein:

[0010] Figure l is a schematic representation of a solvent mist in nitrogen carrier gas being introduced into a catalytic reactor;

[0011] Figure 2 is a graphical representation of an experiment in accordance with Comparative Example 1, depicting the efficacy of oil removal by a hot strip process vs solvent mist in nitrogen carrier gas (i.e., IN2ERT Catalyst Decontamination) (present invention).

[0012] Figures 3 and 4 are a depiction of modeled reactor decontamination and cool-down times, for a nitrogen hot strip (of the related art) vs. solvent mist in nitrogen (i.e. IN2ERT of the present invention).

Detailed Description of the Invention:

[0013] In a surprising finding, it has been found that oils and heavy hydrocarbon deposits can be effectively removed from catalyst beds by treatment with a mist of liquid solvent in nitrogen carrier gas. Nitrogen can be provided from a nitrogen source such as a nitrogen pumper, nitrogen generator, a trailer mounted nitrogen vaporizer unit, high pressure nitrogen cylinders or tubes, a nitrogen pipeline, or a combination of nitrogen source options and delivered to reactor at a controlled mass or volumetric flow rate. The solvent is provided from a solvent source such as a chemical tote or drum or tanker and is also delivered in a controlled mass or volumetric flow rate. Total flow ranges are dependent on the system to be purged or decontaminated and could vary from 20,000 over 1 million standard cubic feet per hour (scfh). Preferably the solvent is a relatively high boiling non-aqueous hydrocarbon or oxy-hydrocarbon such as a naturally derived terpene. D-Limonene is a preferred solvent having a boiling point of approximately 332°F at 0 psig, increasing to approximately 490°F at 50 psig and approximately 680°F at 300 psig, as predicted by thermodynamic modeling. The solvent is misted into nitrogen carrier gas at moderate temperatures in the range of approximately 100 to 400°F, pressures in the range of about 50 to 500 psig and at a mass flow ratio to nitrogen in the range of approximately 0.1 :1 to 8: 1, whereupon the majority of the solvent remains in the liquid phase. Preferred solvents can have associated autoignition temperatures as part of their physical properties and it is preferred that the treatment temperature is below the auto-ignition temperature of the respective cleaning solvent during treatment. For example, the preferred solvent D-limonene, a naturally occurring terpene has an auto ignition temperature of 459°F, hence the treatment temperature is preferred to be below about 450°F.

[0014] The solvent mist in nitrogen is conveyed to the target reactor via inlet piping and/or temporary hoses, with the reactor typically being at a similar temperature to the inlet solvent mist in nitrogen stream, or optionally up to 200°F hotter. Previously, the IN2ERT, Accelerated Purging and Equipment Cleaning process has been used to effectively decontaminate vapor spaces and clean equipment surfaces, whereas now, the IN2ERT, Catalyst Decontamination process has also been found to be effective at decontaminating packed beds of granular materials having high surface area and porosity, which present a higher degree of difficulty when it comes to contaminant removal. These granular materials include catalysts, adsorbents and reactive getter materials.

[0015] The reactor is first de-inventoried of product, then partially cooled to moderate temperature with nitrogen gas or by conventional refinery cooling operations. With reference to Figure 1, the chemical solvent 100 is introduced into the nitrogen stream 101 via a high shear mixer 102, such as a nitrogen-driven eductor, a spray nozzle, an orifice, or tee or any suitable device or other fluid flow arrangement that creates a fine mist of liquid droplets of the solvent dispersed in nitrogen. The mist is typically carried into the top of the reactor 103 via inlet piping by the nitrogen stream where it enters the reactor 103 and first contacts the top of the catalyst bed 104. Optionally, the solvent in nitrogen mist can be injected at multiple points into the catalyst bed to further improve contacting and contaminant removal. The flow of mist is sustained for approximately thirty minutes to four hours, during which time the solvent contacts the catalyst bed, substantially solubilizing oils and heavy hydrocarbon contaminants, and removing them with the flow of nitrogen gas. After the solvent has been added, the solvent flow is stopped and the flow of nitrogen is preferably continued to further carry the solvent through the catalyst bed. The combined solvent and oil /heavy hydrocarbon effluent can be removed from the nitrogen gas downstream of the catalyst bed by cooling, condensing and phase separation for example. [0016] As will be understood by those skilled in the art, the catalyst bed will act like a filter to separate out the solvent mist from the nitrogen gas, providing contact of the liquid solvent with contaminants in the upper portion of the catalyst bed and thereby solubilizing them. The solvent being a liquid below its boiling point (approximately 490 to 680°F over the pressure range 50 to 500 psig) but applied at moderate temperature in nitrogen (100 to 400°F) has significant vapor pressure, also causing a portion of it to vaporize and be carried further down the catalyst bed in the vapor phase, whereupon it contacts more contaminants solubilizing them and effecting removal. Some of the solvent will also be transported lower in the bed as a mist, or as coalesced liquid. Over the decontamination period, contaminants are removed from the top of the bed down, until substantially all contaminants are removed. The application of the solvent as a liquid phase mist has several advantages, including:

(i) the ability to introduce a large volume of solvent to the reactor in a relatively short amount of time;

(ii) the ability to transport the liquid solvent in a carrier gas to the reactor and disperse the solvent across the catalyst cross-section;

(iii) the filtering out of the liquid mist by the catalyst bed, causing the solvent to be held up by the bed increasing residence time and contact time with the contaminants;

(iv) by subsequent evaporation in the catalyst bed, the solvent also acts to further remove heat from the catalyst bed, which can add to the cooling effect of the nitrogen carrier gas; and

(v) when combined with nitrogen cool-down before, during and after chemical mist injection, there is a seamless integration of both the decontamination and cool-down processes, presenting time savings.

[0017] After the heavy contaminants have been substantially removed with the solvent, nitrogen continues to flow through the reactor to desorb remaining light hydrocarbons and EES (LELs). The nitrogen can also be used to simultaneously cool the reactor, to save time. Again, pressures for decontamination and cooling are typically in the 50 to 500 psig range and can be varied during these processes. Accounting for minimum reactor pressure to push any residual liquids, pressure drop due to piping and any ancillary equipment, the minimum pressure typically used in reactor systems is 50 psig. Desorption of light LELs from the catalyst for example will be more effective at lower pressures in this pressure range. [0018] The method described above, in an exemplary embodiment comprises once through cooling of a reactor where cold nitrogen is supplied from a nitrogen supply source and delivered at a temperature in the range of 40-3 OOF after the decontamination process. Cooling down of reactors containing catalysts with significant mass is rate limited after 300 F. This can be sped up to provide an enhanced cooldown using colder nitrogen. Utilization of colder nitrogen is also sometimes referred to assisted cooldown. The cooling method in the exemplary embodiment includes:

I. Completion of the decontamination process to remove any oils bound to catalyst particles

II. Supplying nitrogen from a nitrogen source such as a nitrogen pumper in the range of 40F -300F to a reactor system to cool said system to 100 F in less time than an unassisted cool down.

III. Continuing to flow cold nitrogen gas until LELs in the exiting gas stream reach <20% of the lower explosive limit.

[0019] The method described above, can also be through direct cooling of the reactor system wherein the system is cooled with a cooling stream routed from a non-mechanical pump where the cooling stream is a combination of a vaporized motive fluid stream with at least a portion of an effluent gas stream from the unit operation wherein the cooling method includes: i. circulating a portion of the effluent stream with the non-mechanical pump wherein the vaporized motive fluid provides motive force ii. combining the effluent stream and vaporized motive fluid in the non-mechanical pump to deliver a combined stream temperature in the range of 40 to 3 OOF iii. adjusting the mass ratio of the flow rates of the unit operation effluent; and iv. continuing to flow nitrogen until the LELs in the exiting gas stream reach < 20% of the lower explosive limit, and preferably <10%.

[0020] In another embodiment, the method is carried out by direct cooling the reactor system wherein the system is cooled with a cooling stream routed from a non-mechanical pump where the cooling stream is a combination of a vaporized motive fluid stream with at least a portion of an effluent gas stream from the unit operation wherein the cooling method includes: i. circulating a portion of the effluent stream with the non-mechanical pump wherein the vaporized motive fluid provides motive force ii. combining the effluent stream and vaporized motive fluid in the non-mechanical pump to deliver a combined stream temperature in the range of 40F to 3 OOF; and iii. adjusting the mass ratio of the flow rates of the unit operation effluent; and continuing to flow nitrogen until the LELs in the exiting gas stream reach < 20% of the lower explosive limit.

[0021] In yet a further embodiment, the method is carried out by the steps outlined above, and sparging or injecting liquid nitrogen from a liquid nitrogen source directly into the effluent stream from reactor system to reduce the effluent stream temperature to 40F to 3 OOF; and ; continuing to flow cold nitrogen gas until the LELs in the exiting gas stream reach < 20% of the lower explosive limit.

[0022] To conclude, and with reference to the examples, the solvent mist decontamination process is effective at oil and heavy hydrocarbon removal and presents opportunities to save, time, nitrogen and solvent volumes, especially when combined with nitrogen cool-down. Light LEL desorption with nitrogen or other pure gases (hot stripping) is well known in the art and whilst not illustrated here, is fully expected to be enhanced by the substantial removal of oil and heavy hydrocarbons of the present invention.

[0023] The invention is further explained through the following examples which compare to the related art and should not be construed as limiting the present invention.

[0024] Example 1: The decontamination process was tested in a laboratory setting, using gamma alumina particles that were soaked in oil for 72 hours. In this specific example, nitrogen hot strip, and the IN2ERT catalyst decontamination processes were compared. All tests use oil- soaked alumina (55g). Reactor dimensions were Height, H = 10 in x Diameter, D = 0.875 in, with a volume of 98.5 ml filled with oil-soaked alumina. For the nitrogen hot strip, the decontamination time was 2 hours. In this method, hot nitrogen only was used to remove oil from the catalyst beads. The nitrogen flowrate was 100 seem, at a pressure of 300 psig and reactor temperature of 200° F. In the IN2ERT reactor decontamination case, various experiments were carried out wherein the decontamination treatment was performed with different solvent loadings in nitrogen. The total solvent delivered ranged between 5 and 115 ml. The nitrogen flowrate of 100 seem stayed the same. For comparison to hot stripping, the decontamination treatment was also performed for 2 hours. The results are shown in Figure 2, where is can be seen that up to 90% of the oil was removed from the catalyst bed, compared to only 50% removal with the hot nitrogen strip, as determined by a material balance [0025] Example 2: The IN2ERT catalyst decontamination process was simulated in conjunction with the nitrogen cool-down process for an example reactor. The conditions and results are depicted in Figure 3 and 4 vs hot nitrogen stripping vs vapor phase cleaning alternatives. Heat up and cool down models were performed using a proprietary Linde Services Engineering program. Comparative analysis was done for two specific cases, a) When the reactor is hot (500 °F) and requires decontamination and b) When the reactor has been partially cooled down already (250 °F). It can be seen that:

(i) When the reactor is at 500 °F, hot nitrogen stripping takes 78 hours to hot strip and cool down the reactor to 100 °F. The IN2ERT catalyst decontamination process saves at least 3 hours compared to vapor phase cleaning and provides 12-24 hours of time savings compared to hot N2 stripping.

(ii) If the reactor is already partially cooled to start with as can be the case in turnaround scheduling, Linde, IN2ERT liquid phase decontamination can save 3-4 days compared to N2 hot stripping process and up to 2 days compared to vapor phase cleaning. An additional benefit is >50 % N2 savings vs alternatives, when implemented at a lower temperature. IN2ERT catalyst decontamination can be completed at lower temperatures versus the alternatives. This enables quicker treatment versus requiring heat up time to reach vapor phase or hot stripping temperatures. Reactor information on which heat up and cooldown models were performed is as follows:

Example Reactor Information eactm Type: Naphtha Hydrotreater

Unit Capacity crude

Total weight 284S90 lbs (1 GSSOG catalyst)

[0026] Assumed reactor pressure 200 psig; Once through N2 cooling rate 160,000 scfh; hot N2 heating rate 100,000 scfh. Equivalent chemical usage assumed for both vapor phase and liquid phase processes.